Liquid crystalline polymer compositions process, and products

ABSTRACT

Novel compositions comprising a high concentration of one or more extended chain homopolymer, copolymer, or block polymer and certain polyphosphoric acids are prepared. Such compositions are optically anisotropic (liquid crystalline), capable of exhibiting excellent cohesive strength, and are especially suited to the production of high molecular weight ordered polymer fibers by dry-jet wet spinning. These liquid crystalline compositions are capable of being drawn through long air gap distances and spun at exceptionally high spin draw ratios. Fibers, films and other articles formed from these liquid crystalline compositions exhibit exceptionally high physical and heat resistant properties.

ORIGIN OF INVENTION

This invention was made with Government support under under U.S.Department of Defense contract Nos. F33615-81-K-5070, F49620-81-K-0003,and/or F33815-82-C-5079 awarded by the United States Air Force. TheGovernment has certain rights in this invention.

This application is a continuation of Ser. No. 06/733,424, filed May 13,1985 now U.S. Pat. No. 5,260,365; which is a continuation of Ser. No.06/616/469, filed Sep. 15, 1983 now U.S. Pat. No. 4,533,693; which is acontinuation-in-part of Ser. No. 06/433,831, filed Sep. 17, 1982 nowU.S. Pat. No. 4,533,692.

TECHNICAL FIELD OF INVENTION

The present invention relates broadly to novel anisotropic(liquid-crystalline) extended chain polymer-polyphosphoric acidcompositions, to the production of high molecular weight extended chainpolymers by polycondensation of selected monomers in certainpolyphosphoric acids, and especially to the production of highlyconcentrated polymer compositions from which industrially usefulpolymeric articles such as fibers and films are readily produced.

Among some of the most serious difficulties encountered in theproduction of thermally stable articles such as fibers and films fromextended chain polymers are described in the Background Art below.

REFERENCE TO RELATED APPLICATIONS

Reference is made to other pending PCT International and U.S. patentapplications all assigned to SRI International and having as one oftheir inventors, James F. Wolfe. Said other applications are entitled:"Liquid Crystalline Poly(2,6-benzothiazole) Compositions, Process, andProducts", and "Liquid Crystalline Polymer Compositions, Process, andProducts" and having International Application Numbers PCT/US82/01286and PCT/US82/01285 respectively. This application is acontinuation-in-part of PCT/US82/01285, 17 Sep. 1982. The pending PCTInternational and United States patent applications are hereinincorporated by reference.

BACKGROUND ART

In general, the class of aromatic heterocyclic extended chain polymersare well known for their outstanding thermal, physical, and chemicalproperties. Unfortunately, these polymers are essentially non-meltingand have proven very difficult to economically process into articles. Inorder to fashion such polymers into desired articles of commerce, forexample fibers, films, fibrids, and the like, it is necessary that theybe in solution or dope form. Although such polymers can be dissolved invarious acidic solvents, such as sulfuric acid, methanesulfonic acid,chlorosulfonic acid, polyphosphoric acid, and the like, difficulty isoften experienced in preparing and using the polymer-acid compositionsor dopes because of poor polymer-acid solubility.

Normally, a precipitated or dried particulate form of the polymer isdissolved in a strong acidic solvent by mixing the (isolated) polymerparticles at elevated temperatures and/or under high pressures for aperiod from several hours to several days. If the polymer is insolublein the particular solvent, other solvents or various solvent mixturesare employed. Usually, heating and cooling cycles are applied andrepeated to obtain a useful dope.

The resulting dopes often contain undissolved polymer and must befiltered before further processing into articles.

Although spinning dopes of polybenzobisoxazole, polybenzimidazole andpolybenzobisthiazole in sulfuric acid and/or methanesulfonic acid and/orchlorosulfonic acid with polymer concentrations above about 10 percentare known in the art, the intrinsic viscosity of these polymers is forthe most part below 5 dL/g and oftentimes less than 3 dL/g. The cohesivestrength of such dopes is inherently weak and economically lessdesirable for use in dry-jet wet spinning. In the case ofpolybenzobisoxazole, numerous attempts of dry-jet wet spinning anapproximately 10% polybenzobisoxazole/methane sulfonic acid-dope intofibers were not successful (E. W. Choe, et al., in Macromolecules 1981,14, pp 920-924).

In the case of polybenzimidazole, prior art dopes of this polymer lackadequate strength to maintain filament integrity while dropping throughthe air-gap. In order to overcome this problem U.S. Pat. No. 4,263,245teaches dissolving a high concentration (up to 30%) of this polymer intosuitable solvents such as concentrated sulfuric acid. At such highpolymer concentrations lithium chloride is required to prevent thepolybenzimidazole from phasing out of solution.

In the case of polybenzobisthiazole, U.S. Pat. No. 4,225,700 teaches theformation of a liquid crystalline composition of this polymer atconcentrations near 10% in methane sulfonic acid and chlorosulfonic acidand at about 6% in polyphosphoric acid. Concentrations ofpolybenzobisthiazole in polyphosphoric acid above about 10% by weightare difficult, if indeed possible to achieve. One difficulty encounteredis that the solution of the 2,5-diamino-1,4-benzenedithiol monomer inpolyphosphoric acid with the P₂ O₅ content described in U.S. Pat. No.4,225,700 is very viscous sad dehydrohalogenation is difficult. Alsoconsiderable foaming results. Although solutions of precipitated polymerin solvents such as methane sulfonic acid and chlorosulfonic acid can beprepared, high concentrations of polymer are difficult or impossible toachieve. S. R. Allen, et al., in Macromolecules 1981, 14, pp. 1135-1139describes attempts at spinning polybenzobisthiazole directly from thepolymerization medium (polyphosphoric acid) containing 5-6% polymer.

Insofar as polybenzobisthiazole is concerned it is possible to obtaincompositions near to 10% of the polymer in polyphosphoric acid withintrinsic viscosity equal to 26 dL/g (J. F. Wolfe, et al.,Macromolecules 1981, 14, pp. 915-920). Attempts to increase theintrinsic viscosity of the polymer can only be achieved at a majorsacrifice (decrease) in polymer concentration. Liquid crystallinecompositions of 10% polybenzobisthiazole in polyphosphoric acid areheretofore unknown in the art. Liquid crystalline compositions ofpolybenzobisthiazole having intrinsic viscosities greater than about30.3 dL/g in polyphosphoric acid are heretofore unknown in the art.

In practical terms this means that such polymer-polyphosphoric acidcompositions are severely limited in their potential usefulness for theproduction of highly ordered high molecular weight polymeric articles.

In general, liquid crystalline extended chain polymer compositions (withthe exception of polybenzobisthiazole as mentioned above) inpolyphosphoric acid are heretofore unknown in the art; and moreover,liquid crystalline extended chain copolymer and block polymercompositions are heretofore unknown in the art.

DISCLOSURE OF INVENTION

1. Objects of Invention

Accordingly, it is an object of the present invention to providecompositions substantially free of one or more of the disadvantages ofprior art compositions.

Another object is to provide a process for preparing liquid crystallineextended chain polymer compositions.

A further object is to provide liquid crystalline extended chain polymercompositions having excellent cohesive strength.

Another object is to provide liquid crystalline extended chain polymercompositions having excellent spin stretchability.

Another object is to provide liquid crystalline extended chain polymercompositions capable of being drawn through long air gap distances.

Yet another object is to provide liquid crystalline extended chainpolymer compositions capable of being drawn at high spin draw ratios.

A further object of the invention is to prepare a liquid crystallinespinning composition having a high extended chain polymer content.

A still further object is to provide liquid crystalline extended chainhomopolymer compositions.

Another object is to provide liquid crystalline extended chain copolymercompositions.

Yet another object is to provide liquid crystalline extended chain blockpolymer compositions.

Another object of the invention is to provide a method of preparing aliquid crystalline polymer composition having a high polymer content ofan extended chain homopolymer.

Another object of the invention is to provide a method of preparing aliquid crystalline polymer composition having a high polymer content ofan extended chain copolymer.

Another object of the invention is to provide a method of preparing aliquid crystalline polymer composition having a high polymer content ofan extended chain block polymer.

Another object of the invention is to provide a method of preparingliquid crystalline extended chain polymer compositions from selectedmonomers.

Another object is to provide a process for preparing liquid crystallinehigh molecular weight extended chain polymer compositions.

A further object of the invention is to provide a method forsynthesizing high molecular weight extended chain homopolymers.

A further object of the invention is to provide a method forsynthesizing high molecular weight extended chain copolymers.

A further object of the invention is to provide a method forsynthesizing high molecular weight extended chain block polymers.

A still further object is to provide a method whereby thedehydrohalogenation of certain hydrohalide monomers may be carried outmore easily and rapidly.

Yet another object is to provide a method whereby a substantially higherconcentration of monomeric reactants can be employed which results inliquid crystalline extended chain polymer compositions of considerablyhigher polymer concentration than has been possible heretofore.

Another object is to alleviate the foaming problem referred to above.

Another object is to provide articles prepared from liquid crystallineextended chain polymer compositions.

A further object of the invention is to prepare articles such as fibersand films from a liquid crystalline polymer composition comprisingselected extended chain homopolymers.

A further object of the invention is to prepare articles such as fibersand films from a liquid crystalline polymer composition comprisingselected extended chain copolymers.

A further object of the invention is to prepare articles such as fibersand films from a liquid crystalline polymer composition comprisingselected extended chain block polymers.

Another object of the invention is to provide a process for thecontinuous production of extended chain homopolymer, copolymer, andblock polymer articles such as fibers and films starting with selectedmonomers.

The above and other objects of the invention will be apparent from theensuing description and the appended claims.

2. Statement of Invention

In accordance with our discovery, the present invention broadlyencompasses novel polymer compositions which are useful as dopes in theproduction of high strength shaped articles comprising blends of certainpolyphosphoric acids, as described hereinafter, and a high concentrationof one or more high molecular weight extended chain polymers having oneor more mesogenic group or groups. The extended chain polymers can behomopolymers, copolymers, or block polymers, as exemplified hereinafter.The extended chain polymer is present in the blend at a sufficientconcentration so as to be capable of exhibiting an anisotropic polymerphase alone or in combination with one or more different polymers withor without mesogenic group or groups. The blends according to theinvention are polycondensation products obtained by reaction of selectedmonomers in an appropriate solution of phosphoric acid, as describedhereinafter. These blends exhibit special properties which make themvery useful as dopes in the production of fibers, films, fibrids, andthe like. In addition to being anisotropic (liquid-crystalline), theblends have a novel combination of properties including unexpectedlyhigh spin-stretchability and excellent cohesive strength, as well ashaving the capability of being drawn through short, as well as extremelylong, air-gap distances, and spun at low, as well as exceptionally high,draw ratios. It is believed that these properties can be attributed tothe combination of high polymer concentration, high polymer molecularweight, and a high phosphorus pentoxide content comprising the blends ofthe present invention.

Our discovery further broadly encompasses a process for preparing novelextended chain polymer compositions which are useful as dopes in theproduction of fibers and films. This process comprises:

(a) mixing at least one of a selected first monomer (as describedhereinafter) with or without oxidation protecting atoms or groups with apreliminary solvent of phosphoric acid having a relatively lowphosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a first mixture of the first monomer in the preliminarysolvent,

(c) adding at least one of a selected second monomer (as describedhereinafter) in the resulting mixture of step (b) to provide a firstmixture of the first and second monomer in the preliminary solvent,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (b) or (c) to provide a first or a first and secondmonomer reaction medium of greater phosphorus pentoxide content suitablefor polymerization,

(e) causing polymerization of the first or the first and second monomerat a temperature sufficient to effect reaction at a rate to form a firsthomo-oligomeric product or a first co-oligomeric product having apreselected intrinsic viscosity, or

(f) causing polymerization of the first or the first and second monomerat a temperature sufficient to effect reaction at a rate to form a firsthomopolymeric product or a first copolymeric product,

(g) mixing a selected amount of the first homo-oligomeric product with aselected amount of at least one of a selected second homo-oligomericproduct so as to form a first poly-oligomeric product, the secondhomo-oligomeric product being formed by like steps (a) and (b) followedby:

(1g) adding at least one of a selected second monomer in the resultingmixture of step (b) to provide a mixture of a first and second monomerin the preliminary solvent,

(2g) then increasing the phosphorus pentoxide content of the mixtureresulting from step (b) or (1g) to provide a first or a first and secondmonomer reaction medium of greater phosphorus pentoxide content suitablefor polymerization,

(3g) causing polymerization of the first or first and second monomer ata temperature sufficient to effect reaction at a rate to form the secondhomo-oligomeric product having a preselected intrinsic viscosity,

with the overall proviso that at least one of the selected monomers ofstep (a) or (1g) which forms the second homo-oligomeric product bedifferent from at least one of the selected monomers of step (a) or (c)which forms the first homo-oligomeric product, or

(h) mixing a selected amount of the first homo-oligomeric product with aselected amount of a second mixture of at least one of a selected firstmonomers or a first and second monomer in the preliminary solvent so asto form a monomer-oligomer mixture, and then increasing the phosphoruspentoxide content of the monomer-oligomer mixture to provide amonomer-oligomer reaction medium of greater phosphorus pentoxide contentsuitable for polymerization, the first monomer of the second mixturebeing formed by like steps (a) and (b) and the first and second monomerof the second mixture being formed by like steps (a), (b) and (c), withthe overall proviso that at least one of the selected monomers of step(a) or (c) which forms the first or first and second monomer of thesecond mixture, be different from at least one of the selected monomersof step (a) or (c) which forms the first homo-oligomeric product,

(i) causing polymerization of the poly-oligomeric product resulting fromstep (g) or the monomer-oligomer resulting from step (h) at atemperature sufficient to effect reaction at a rate to form a firstblock-oligomeric product having a preselected intrinsic viscosity or afirst block-polymeric product,

(j) spinning, drawing, extruding, or casting an article from said firsthomo-oligomeric product, said first co-oligomeric product, said firsthomopolymeric product, said first copolymeric product, said firstpoly-oligomeric product, said second homo-oligomeric product, said firstblock-oligomeric product, said first block-polymeric product, ormixtures thereof.

2a. Figures

The invention will be more fully explained with reference to the Figureswherein:

FIG. 1 graphically illustrates the weight stability of as spun polymerfibers of --BI--_(n) (Example 13) and --AI--_(n) (Example 12) with timeduring isothermal aging in circulating air at 371° C.;

FIG. 2 graphically illustrates the weight stability of precipitatedpolymers of --V--_(n) (Example 120) and --T--_(n) (Example 27) with timeduring isothermal aging in circulating air at 371° C.;

FIG. 2a graphically illustrates the weight stability by TGA of blockcopolymers AI-AN" (Example 74) and AI-AG" (Example 73) with temperaturein air at a heating rate of 5° C. per minute;

FIG. 3 graphically illustrates the weight stability by TGA of polymers--T--_(n) (Example 27) and --V--_(n) (Example 120) with temperature inhelium at a heating rate of 5° C. per minute;

FIG. 4 graphically illustrates the weight stability by TGA of polymers--BI--_(n) (Example 13) and --AI--_(n) (Example 12) with temperature inhelium at a heating rate of 5° C. per minute;

FIG. 5 graphically illustrates the weight stability by TGA of polymers--T--_(n) (Example 27) and --V--_(n) (Example 120) with temperature inair at a heating rate of 5° C. per minute;

FIG. 6 graphically illustrates the weight stability by TGA of polymers--BI--_(n) (Example 13) and --AI--_(n) (Example 12) with temperature inair at a heating rate of 5° C. per minute;

FIG. 7 graphically illustrates the relationship of amount of useable PPAand % P₂ O₅ content required to achieve f of 0.822 for selected polymerconcentrations P_(c) (plot of equation a*) showing a region (shaded dasharea) of poor solubility for monomer 1a;

FIG. 8 graphically illustrates the % P₂ O₅ content profile for a 14.8 wt% --AI--_(n) polymerization (Example 2) showing the limits of achievablemolecular weight when starting with a high P₂ O₅ content preliminarysolvent;

FIG. 9 graphically illustrates the % P₂ O₅ content profile for a 8.6 wt% --T--_(n) polymerization (Example 3) showing limits of achievabledegree of polymerization when starting with a high P₂ O₅ contentpreliminary solvent;

FIG. 10 graphically illustrates a typical % P₂ O₅ content profile for a14.5 wt % --AI--_(n) polymerization (Example 12) showing the advantagesof the Invention when starting with a low P₂ O₅ content preliminarysolvent followed by an increase of P₂ O₅ content at the start ofpolymerization;

FIG. 11 graphically illustrates a typical % P₂ O₅ content profile for a13.0 wt % --BI--_(n) polymerization (Example 13) showing the advantagesof the invention when starting with a low P₂ O₅ content preliminarysolvent and step-wise addition of P₂ O₅ followed by an increase of P₂ O₅content at the start of polymerization;

FIG. 12 graphically illustrates a typical % P₂ O₅ content profile for a20.3 wt % --T--_(n) polymerization (Example 27) showing the advantagesof the invention when starting with a low P₂ O₅ content preliminarysolvent followed by an increase of P₂ O₅ content at the start ofpolymerization;

FIG. 13 graphically illustrates a typical % P₂ O₅ content profile for a16.87 wt % --V--_(n) polymerization (Example 122) showing the advantagesof the invention when starting with a low P₂ O₅ content preliminarysolvent followed by an increase of P₂ O₅ content at the start ofpolymerization;

FIG. 14 is a % P₂ O₅ profile diagram giving the profile are a bounded byABCDEFGHI of % P₂ O₅ for achieving the advantages of this invention.

3. Mode(s) for Carrying Out the Invention

The extended chain polymers of the compositions of the present inventionare a class of polymers that can obtain a substantial degree of shapeanisotropy in the liquid state due to restricted rotation of bonds inthe polymer backbone and/or appropriate catenation geometry of rigidbackbone segments. The degree of shape anisotropy is generally definedby the axial ratio, (roh)/d, where -p- is the persistence length of thechain and d is the diameter of the chain. For extended chain polymers,-p- may be substantially the same as or greater than the contour lengthl of the polymer. In the case of a rigid rod polymer, -p- is essentiallyinfinite and the axial ratio is l/d.

By the method of the present invention, it is possible to prepare liquidcrystalline compositions of extended chain homopolymers, copolymers, orblock polymers containing 15 percent or more of polymer. As will appear,the invention is applicable to the preparation of liquid crystallineextended chain polymer compositions of lower polymer concentration butthere are special advantages to preparing compositions of highconcentration.

Extended chain polymer-polyphosphoric acid compositions of such higherpolymer concentration are advantageous.

For example, if the polymer is one, such as polybenzobisthiazole,polybenzobisoxazole, and polybenzobisimidazole, capable of formingliquid crystalline compositions at low concentration (e.g., 5-10%), thatis, if the critical concentration necessary for formation of theanisotropic phase is low, compositions of even higher polymerconcentration can be spun to produce a better quality, higher strengthfiber. We believe this results, in part at least, from a more fullyanisotropic composition and improved composition integrity. Theseimprovements allow greater drawing in the air-gap, improve thecoagulation characteristics, which leads to fewer flaws, and increasepolymer throughput when a liquid crystalline composition is spun by adry-jet-wet spinning technique into a polyphosphoricacid-solvent/polymer-nonsolvent such as methanol, water, or diluteaqueous acid(s).

If the polymer is one, such as poly (2,6-benzothiazole) that is lessrodlike in structure than polybenzobisthiazole or polybenzobisoxazoleand thus possesses a critical concentration for anisotropic phaseformation greater than 10% and in the region of concentrations of thisinvention, extruding of these heretofore unattainable solutions producesa dramatic increase in strength and modulus because of the ordering ofthe polymer during this fabrication.

These advantages result in a more highly ordered, lower-defect fiberthan results from spinning a less concentrated composition of polymers.

Another advantage of preparation of these polymers in the anisotropicphase is a considerable increase in the molecular weight of the polymerobtained.

Preliminarily it is helpful to describe the chemistry of phosphoricacids and strong phosphoric acids or polyphosphoric acids as follows:

As used herein the term "phosphoric acid(s)" means commercial phosphoricacid(s) containing 85-86% H₃ PO₄.

The strong phosphoric acids, or polyphosphoric acids referred to as PPA(polyphosphoric acid) are members of a continuous series of amorphouscondensed phosphoric acid mixtures given by the formula ##STR1## wherethe value of n depends on the molar ratio of water to phosphoruspentoxide present.

Characterization and methods of forming various polyphosphoric acids andexamples of such strong acids useful in accordance with the practice ofthe present invention can be found in the following papers: A. L. Huhtiand P. A. Gartaganis "The Composition of the Strong Phosphoric Acids,"Can. J. Chem., Vol. 34, 1956 pp. 785-797; and J. E. Such, "LinearPolyphosphoric Acids", Mellar's Comprehensive Treatise on Inorganic andTheoretical Chemistry, Vol VIII, Supplement III, pp. 726-753, Wiley1971. The subject matter of these articles are specifically incorporatedherein by reference.

In its most general definition, polyphosphoric acid composition canrange from distributions where the average value of n is less thanunity, giving rise to a mobile liquid, to high values of n, where thepolyphosphoric acid is a glass at normal temperatures. Because thespecies of polyphosphoric acid are in a mobile equilibrium, a givenequilibrium composition can be prepared in many ways. For instance, thesame distribution or polyphosphoric acid composition could be preparedby either starting with concentrated orthophosphoric acid (H₃ PO₄, n=1)and driving off water or by starting with phosphorus pentoxide (P₂ O₅)and adding an appropriate amount of water.

All polyphosphoric acid compositions can be described as a ratio of P₂O₅ and water by reducing the various species present (on paper) to P₂ O₅and water. We will then use the convention that polyphosphoric acidcomposition will be expressed in terms of a P₂ O₅ content (as apercentage) defined as P₂ O₅ content ##EQU1##

Thus, the P₂ O₅ content of pure orthophosphoric acid could be derived byreducing one mole of H₃ PO₄ to 0.5 moles P₂ O₅ +1.5 moles H₂ O.Converting to weights gives the P₂ O₅ content as ##EQU2##

Similarly, the P₂ O₅ content of commercial polyphosphoric acid cam bederived in the following way. Polyphosphoric acid is availablecommercially in two grades, 105% and 115%. These percentages refer to H₃PO₄ content, which means that 100 g of the two grades contain 105 and115 grams of H₃ PO₄. The P₂ O₅ content of 115% polyphosphoric acid canthen be calculated knowing the P₂ O₅ content of 100% H₃ PO₄. ##EQU3##

Freshly prepared polyphosphoric acid as described by Wolfe and Loo U.S.Pat. No. 4,225,700 employed 1.52×g of P₂ O₅ to x grams of 85.6% H₃ PO₄,thus the P₂ O₅ content of that mixture is ##EQU4##

Thus, polyphosphoric acid compositions, by our definition, equivalent tothese three examples could be prepared in principle by starting with P₂O₅ and adding 27.6, 16.7, and 15.1% by weight of water.

Homopolymeric Compositions and their Preparation

In accordance with one aspect of the invention, there is provided aliquid-crystalline composition useful in the preparation of fibers andfilms comprising a polycondensation product consisting essentially of ablend of certain polyphosphoric acids and a high concentration of atleast one high molecular weight extended chain homopolymer having thegeneral formulas: ##STR2## wherein Ar¹ represents an aromatic moiety andis XX as defined below, X₁ and X₂ are the same or different and aresulfur, oxygen, or NR (R being hydrogen or an organic group), thenitrogen atoms and X₁ and X₂ being bonded to aromatic carbon atoms ofAr¹, N and X₁ or X₂ of each hetero ring are disposed ortho to oneanother and Y² is nil or represents a bivalent organic radical and isXXI as defined below, n being a positive integer; ##STR3## wherein Ar³represents an aromatic moiety and is XXII as defined below, X₃ issulfur, oxygen, or NR (R being hydrogen or an organic group), thenitrogen atoms and X₃ being bonded to aromatic carbon atoms of Ar³, Nand X₃ of each hetero ring are disposed ortho to one another, n being apositive integer; ##STR4## wherein Ar¹ represents an aromatic moiety andis XX as defined below, and Ar⁴ represents an aromatic moiety and isXXIII as defined below, the nitrogen atoms being bonded to aromaticcarbon atoms of Ar¹ and the carbon atoms being bonded to aromatic carbonatoms of Ar⁴, n being a positive integer; ##STR5## wherein Ar⁵represents an aromatic moiety and is XXIV as defined below, the nitrogenatoms being bonded to Ar⁵, n being a positive integer; ##STR6## whereinAr⁶ represents an aromatic moiety and is XXV as defined below, Ar¹represents a different aromatic moiety and is XX as defined below, X₁and X₂ are the same or different and are sulfur, oxygen, or NR (R beinghydrogen or an organic group), the NH groups and X₁ and X₂ being bondedto aromatic carbon atoms of Ar⁶ and Ar¹, NH and X₁ or X₂ of each heretoring are disposed ortho to one another, n being a positive integer;##STR7## wherein Ar⁹ represents an aromatic moiety and is XXVI asdefined below, X₄ is sulfur, oxygen, or NR (R being hydrogen or anorganic group), the NH groups and X₄ being bonded to aromatic carbonatoms of Ar⁹, n being a positive integer; ##STR8## wherein Ar¹represents an aromatic moiety and is XXVII as defined below, Y⁷represents an aromatic moiety and is XXVIII as defined below, thenitrogen atoms being bonded to aromatic carbon atoms of Ar¹ and bondedto adjacent carbon atoms of Y⁷, n being a positive integer; ##STR9##wherein Ar¹ represents an aromatic moiety and is XX as defined below, Y⁸is XXIX as defined below, X₁ and X₂ are the same or different and aresulfur, oxygen, or NR (R being hydrogen or an organic group), thenitrogen atoms and X₁ and X₂ being bonded to aromatic carbon atoms ofAr¹ and adjacent carbon atoms of Y⁸, N and X₁ or X₂ of each hetero ringare disposed ortho to one another, n being a positive integer.

The aromatic moieties Ar¹, Ar³, Ar⁴, Ar⁵, Ar⁶, Ar⁹, and Y², Y⁷, and Y⁸of the extended chain polymer formulas above are defined as follows:##STR10##

Any monomeric material or mixture of monomeric materials having theability to react in polyphosphoric acid to form the extended chainpolymers (i.e., the above formulas I-VIII homopolymers, and the variousformulas IX-XIX copolymers and block polymers herein defined in thespecification) of this invention can be utilized.

In general, suitable monomeric materials selected for use in formingliquid-crystalline extended chain polymer compositions of the presentinvention are of nine types as described below. Type 1, 2, 4, 6, 7, and8 are homo-bifunctional monomers. Type 3, 5, and 9 arehetero-bifunctional monomers.

Type 1 monomers have the general formula ##STR11## wherein Ar¹ is anaromatic moiety; X₁ and X₂ are the same or different atoms or groupsselected from the class O, S, and NR; R is hydrogen or an organic groupattached to N; the R's on the two nitrogen atoms where both X₁ and X₂are NR may be the same or different; NH₂, X₁ H and X₂ H are bonded toaromatic carbon atoms of Ar¹ ; the groups on the left side of Ar¹ areortho with respect to one another and the groups on the right side ofAr¹ are ortho with respect to one another.

The two sets of NH₂ and XH are positioned on Ar¹ such that they do notboth interact partially with the appropriate condensing moiety ofanother monomer. Monomer 1 is typically isolated as a hydrohalide saltof the monomer.

In general, Ar¹ may be any aromatic moiety (carbocyclic or heterocyclic)and it may be a single ring such as ##STR12## or it may comprise aplurality of aromatic rings connected by valence bonds or by linkingatoms or groups such as ##STR13## where β is a valence bond (as indiphenyl) or a divalent atom (--O-- or --S--) or group such as--NR--(R═H or an organic group). --(CH₂)-- (n=1 or a higher integer).Specific examples of Ar¹ are as follows: ##STR14##

The aromatic ring or rings of Ar¹, such as those described above andothers, may bear one or more substituent. These substituents, which maybe organic or inorganic may be or may contain hetero atoms, may be anyatom or group which is compatible with the reactant, the solvent, thepolycondensation reaction and the resulting oligomer or polymer.Substituents which are chemically reactive with Types 2 thru 9 monomers(see below), with the solvent (PPA) or with the oligomeric or polymericproducts are to be avoided. Also, substituents which offer sterichindrance to the polycondensation are to be avoided.

Among permissible hydrocarbon substituents are alkyl (e.g., C₁ to C₁₀straight chain and branched chain alkyl, benzyl, etc.), phenyl, chlorosubstituted alkyl, phenyl and benzyl. Among permissible heretosubstituents are chloro, bromo, nitro, alkoxy, aryloxy, SO₃ H, SR, and--NR₁ R₂ (R₁ and R₂ being organic groups).

Formula 1 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention may alsofurther be classified into three groups: Class 1 (1,1), Class 2 (1,2),and Class 3 (1,3). The first number of the number pairs denotes themonomer type and the second number of the pairs denotes the monomerclass.

The preferred (1,1) monomers are those wherein Ar¹ is a six-memberedaromatic ring with the four valence positions being on carbon atomshaving a 1, 2, 4, 5 relationship to each other, such as 1, 2, 4,5-benzene or 2, 3, 5, 6-pyridine; R is H or a monovalent aromaticradical, such as phenyl, or a monovalent heteroaromatic radical, such as2-pyridyl, or a monovalent aliphatic radical, such as methyl. Monomers(1,1) which when reacted with a diacid or a diacid derivative give twosubstantially collinear bonds are most preferred.

Specific examples of (1,1) monomers preferred for use in the inventioninclude those monomers (shown as hydrohalides) in Table 1 below.

                  TABLE 1                                                         ______________________________________                                        Monomers of Type 1, Class 1                                                   ______________________________________                                         ##STR15##                                                                    2,5-diamino-1,4-benzenedithiol dihydrochloride                                obtained according to Wolfe, et al.,                                          Macromolecules, Vol. 14, Page 915 (1981).                                      ##STR16##                                                                    4,6-diamino-1,3-benzenediol dihydrochloride                                   obtained from 4,6-dinitro-1,3-benzenediol                                     according to Wolfe, et al., Macromolecules, Vol.                              14, Page 909 (1981).                                                           ##STR17##                                                                    1,2,4,5-tetraaminobenzene tetrahydrochloride                                  obtained from Aldrich Chemical Co. and purified                               by recrystallization from dilute HCl by heating,                              adding charcoal, filtering, and adding                                        concentrated HCl.                                                              ##STR18##                                                                    2,5-diamino-1,4-benzenediol dihydrochloride                                   prepared according to Wolf, et al., J. Polymer                                Sci., Part A-1, Vol. 6, page 1503 (1968).                                      ##STR19##                                                                    2,3,5,6-tetraaminopyridine trihydrochloride                                   prepared by the dinitration of 2,6-diamino                                    pyridine, followed by hydrolysis and reduction by                             the method of A. H. Gerber, J. Polymer Sci.,                                  Polymer Chemistry Ed., Vol. 11, page 1703 (1973).                              ##STR20##                                                                    3,5-diamino-2,6-pyridinediol trihydrochloride                                 prepared by dinitration of 2,6-dimethoxy pyridine                             according to C. D. Johnson, et al., J. Chem. Soc.                             (B), 1967, page 1204, followed by reduction and                               dealkylation.                                                                  ##STR21##                                                                    3,6-diamino-2,5-pyridinedithiol dihydrochloride                               prepared from commercially available 2,5-                                     diamino-pyridine by methods analogous to the                                  preparation of 1a.                                                             ##STR22##                                                                    N.sup.1,N.sup.5 -diphenyl-1,2,4,5-tetraaminobenzene dihydrochloride           prepared starting from  .sub.-- m-dichlorobenzene                             according to H. Vogel and C. S. Marvel, J.                                    Polym. Sci., A, Vol. 1, page 1531 (1963) and                                  purified from toluene before use.                                             ______________________________________                                    

The preferred (1,2) monomers are those wherein Ar¹ is two six-memberedaromatic rings attached by a covalent carbon-carbon bond each withvalences on carbon atoms in the 3 and 4 positions, such as3,3',4,4'-biphenyl or 4,4', 5,5'-(2,2'-bipyridyl), or Ar¹ is two fusedsix-membered rings with valence positions being on carbon atoms andhaving a 1,2,5,6 relationship to each other, such as1,2,5,6-naphthalene.

The four functional groups attached to the valence positions of Ar¹ bycovalent bonds comprise two amino groups and the groups -X₁ H and -X₂ Hsuch that one amino group is ortho to -X₁ H and the other amino group isortho to X₂ H and X₁ H is attached to either the 3 or 4 position in thefirst case or the 1 or 2 position in the second case and -X₂ H isattached to either the 3' or 4' position in the first case and the 5 or6 position in the second case. X₁ and X₂ are defined as above.

Specific examples of (1,2) monomers preferred for use in the inventioninclude those monomers (shown as hydrohalides) in Table 2 below.

                  TABLE 2                                                         ______________________________________                                        Monomers of Type 1, Class 2                                                   ______________________________________                                         ##STR23##                                                                    3,3'-dimercaptobenzidine dihydrochloride                                      prepared by the method of Houben-Weyl, Methoden                               der Organischen Chemie, E. Miller, Ed., Vol IX,                               page 39 (1955).                                                                ##STR24##                                                                    3,3'-dihydroxybenzidine dihydrochloride                                       prepared by the method of C. G. Vogt and F.                                   Marschall, U.S. Pat. No. 2,497,248 (1950) from  -o-                           dianisidine and aluminum chloride.                                             ##STR25##                                                                    3,3'-diamino-4,4'-dihydroxybiphenyl dihydrochloride                           prepared by the method of Y. Imai, I. Taoka, K.                               Uno, and Y. Iwakura, Makromol. Chem, 83, page 167                             (1965).                                                                        ##STR26##                                                                    3,3'-diaminobenzidine tetrahydrochloride dihydrate                            prepared according to (same ref. as for 1h) and                               the tetrahydrochloride recrystallized from dilute                             HCl containing stannous chloride by adding                                    concentrated HCl.                                                              ##STR27##                                                                    3,3'-diamino-4,4'-dianilinobiphenyl dihydrochloride                           prepared from dinitration of 4,4'-                                            dichlorobiphenyl, displacement of the chloro                                  groups by aniline, and reduction.                                              ##STR28##                                                                    1,5-diamino-2,6-naphthalenedithiol dihydrochloride                            by methods analogous to Monomers 1a and 1i.                                    ##STR29##                                                                    1,5-diamino-2,6-naphthalenediol dihydrochloride                               prepared from 2,6-dichloro-1,5-dinitro-                                       naphthalene.                                                                   ##STR30##                                                                    1,2,5,6-tetraminonaphthalene tetrahydrochloride                               prepared by the amination of 2,6-dichloro-1,5-                                dinitro-naphthalene followed by catalytic                                     reduction according to K. Imai, N. Kurihara, L.                               Mathias, J. Wittmann, W. B. Alston, and J. K.                                 Stille, Macromolecules, 6, 158 (1973).                                        ______________________________________                                    

The preferred (1,3) monomers are those wherein Ar¹ is any aromaticmoiety with two sets of ortho-valences at carbon atoms, such as##STR31## wherein β is a bivalent aromatic or heteroaromatic moiety, O,S, SO₂, C═O, --CH₂ CH₂ --, etc.

The four functional groups attached to the valence positions of Ar¹ aredivided into two sets (NH₂ and X₁ H) and (NH₂ and X₂ H) with thefunctional groups within each set being positioned ortho to each otherand the two sets positioned on Ar¹ such that they cannot simultaneouslyreact with the same functional group of another monomer. X₁ and X₂ aredefined as above.

Specific examples of (1,3) monomers preferred for use in the inventioninclude those monomers (shown as hydrohalides or as monomers) in Table 3below.

                  TABLE 3                                                         ______________________________________                                        Monomers of Type 1, Class 3                                                   ______________________________________                                         ##STR32##                                                                    3,3'-dimercapto-4,4'-diaminodiphenyl ether dihydrochloride                    prepared according to the method of V. V.                                     Korshak, E. S. Krongauz, A. P. Travnikova, A. L.                              Rasanov, and A. D. Katsarava, Dokl, Akad. Nauk.                               SSSR, 196, 106 (1971).                                                         ##STR33##                                                                    3,3',4,4'-tetraaminodiphenyl ether tetrahydrochloride                         obtained commercially from Pfaltz & Bauer.                                     ##STR34##                                                                    3,3'-dihydroxy-4,4'-diaminodiphenyl ether                                     is prepared according to the method of S. U.                                  Kantor and J. Sonnenberg, U.S. Pat. No. 3,306,876                             (1967).                                                                        ##STR35##                                                                    3,3'-diamino-4,4'-dihydroxydiphenyl ether                                     prepared according to the method of A. S.                                     Lindsey, S. E. Hunt, and G. K. L. Gibson, U.K.                                Patent No. 1,181,531 (1970).                                                   ##STR36##                                                                    3,3',4,4'-tetraaminodiphenyl sulfone                                          prepared from commercially available 4,4'-                                    diaminodiphenyl sulfone by acetylation,                                       dinitration, hydrolysis, and reduction.                                        ##STR37##                                                                    3,3'-dimercapto-4,4'-diaminodiphenyl sulfone                                  prepared from commercially available 4,4'-                                    diaminodiphenyl sulfone by methods analogous to                               the preparation of 1a and 1i.                                                  ##STR38##                                                                    3,3'-dihydroxy-4,4'-diaminodiphenyl sulfone                                   prepared according to the method of G. I. Barz,                               I. Y. Kardash, and V. S. Yakubovich, Polym. Sci.                              USSR., 8, page 2013 (1967).                                                    ##STR39##                                                                    3,3'-diamino-4,4'-dihydroxydiphenyl sulfone                                   prepared from commercially available 4,4'-                                    dihydroxydiphenyl sulfone by acetylation,                                     dinitration, hydrolysis and reduction.                                         ##STR40##                                                                    3,3',4,4'-tetraaminobenzophenone                                              available commercially from Polysciences, Inc.                                 ##STR41##                                                                    3,6-diamino-1,2-benzenedithiol dihydrochloride                                prepared by isolation of 2,7-diaminobenzo[1,2-                                d;6,5-d']bisthiazole from the scheme to prepare                               1a followed by hydrolysis.                                                    ______________________________________                                    

Type 2 monomers have the general formula

    Z.sub.1 --Y.sup.2 --Z.sub.2                                (2)

wherein Y² is a bivalent organic group and Z₁ and Z₂ areelectron-deficient carbon groups and may be the same or different groupsselected from the following class: ##STR42## (R₁ ═H or an organic groupbonded to N by a carbon

The only requirement of Z₁ and Z₂ is that they react with the X₁ H andX₂ H and with the two hydrogen atoms of the primary amino groups of Type1 monomers to form suitable leaving entities, such as water, hydrogensulfide, hydrogen halide, ammonia, etc.

The bivalent group Y² may be an aromatic group, an acyclic aliphaticgroup, or a cycloaliphatic group, and such groups may be substituted byhydrocarbon groups (aliphatic or aromatic) and by hereto atoms andgroups. In general any of groups described above as substituents of thearomatic ring or rings of Ar¹ may be used subject to the samerestrictions.

Formula 2 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention may alsofurther be classified into three groups: Class 1 (2,1), Class 2 (2,2),and Class 3 (2,3). The first number of the number pairs denotes themonomer type and the second number of the pairs denotes the monomerclass.

The preferred (2,1) monomers are those wherein Y² is nil, or Y₂ compriseat least two carbon atoms to which are attached Z₁ and Z₂ such that thetwo exocyclic bonds between Y² and Z₁ and between Y² and Z₂ have a rigidand fixed relationship to each other and are substantially collinear, orY² may also be a cycloaliphatic group that has at least two carbon atomsto which are attached Z₁ and Z₂ such that the two bonds between Y² andZ₁ and between Y² and Z₂ have a highly preferred relationship to eachother that is substantially collinear. Carboxylic acid derivatives of2j-2q and 2z (as herein described below) such as COOH that decarboxylateat temperatures below that required for polycondensation with Type 1monomers are less preferred.

Specific examples of (2,1) monomers preferred for use in the inventioninclude those monomers in Table 4 below.

                                      TABLE 4                                     __________________________________________________________________________    Monomers of Type 2, Class 1                                                   __________________________________________________________________________     ##STR43##                                                                    terephthalic acid                                                             obtained from Amoco Chemicals Co. and micronized and dried before use.         ##STR44##                                                                    terephthaloyl chloride                                                        obtained from Aldrich and sublimed immediately before use.                     ##STR45##                                                                    1,4-benzenedicarboxamide                                                      prepared from 2b or obtained commercially from Pfaltz and Bauer.               ##STR46##                                                                    terephthalonitrile                                                            obtained from Pfaltz and Bauer.                                                ##STR47##                                                                    trans-1,4-cyclohexanedicarboxylic acid                                        obtained from Aldrich and recrystallized from water.                           ##STR48##                                                                    trans-1,4-cyclohexanedicarboxylic acid chloride                               prepared from 2e.                                                              ##STR49##                                                                    trans-1,4-cyclohexanedicarboxamide                                            prepared from 2f.                                                              ##STR50##                                                                    trans-1,4-dicyanocyclohexane                                                  prepared from 2g.                                                              ##STR51##                                                                    2,5-pyridinedicarboxylic acid                                                 obtained from Aldrich Chemical Co.                                             ##STR52##                                                                    2,6-benzo[1,2-d:4,5-d']bisthiazoledinitrile                                   prepared by diazotization of 2,6-diaminobenzobisthiazole                      (see reference for 1a) followed by treatment with cuprous cyanide.             ##STR53##                                                                    2,6-benzo[1,2-d:5,4-d']bisoxazoledinitrile                                    prepared from the condensation of compound 1b with urea followed by           diazotization as for compound 2j.                                              ##STR54##                                                                    2,6-benzobisimidazoledinitrile                                                prepared as for 2k using compound 1c.                                          ##STR55##                                                                    2,6-benzo[1,2-d:4,5-d']bisoxazoledinitrile                                    prepared as described for 2k using compound 1d.                                ##STR56##                                                                    2,6-pyridobisimidazoledinitrile                                               prepared as for 2k using compound 1e.                                          ##STR57##                                                                    2,6-pyrido[2,3-d:6,5-d']bisoxazoledinitrile                                   prepared as for 2k using compound 1f.                                          ##STR58##                                                                    2,6-pyrido[2,3-d:5,6-d']bisthiazoledinitrile                                  prepared as for 2j, using 2,6-diaminopyridobisthiazole as prepared            in the synthesis of 1g.                                                        ##STR59##                                                                    1,7-diphenyl-2,6-benzobisimidazoledinitrile                                   prepared as for 2k using compound 1h.                                          ##STR60##                                                                    2,6-bis(4-carboxyphenyl)benzo[1,2-d:4,5-d']bisthiazole                        prepared by the condensation of compound 1a with  -p-toluic acid              followed by oxidation.                                                         ##STR61##                                                                    2,6-bis(4-carboxyphenyl)benzo[1,2-d:5,4-d']bisoxazole                         prepared by the condensation of 1b with  -p-toluic acid followed by           oxidation.                                                                     ##STR62##                                                                    2,6-bis(4-carboxyphenyl)benzobisimidazole                                     prepared by a method similar to 2s using 1c.                                   ##STR63##                                                                    2,6-bis(4-carboxyphenyl)benzo[1,2-d:4,5-d']bisoxazole                         prepared by method similar to 2s using 1d.                                     ##STR64##                                                                    2,6-bis(4-carboxyphenyl)pyridobisimidazole                                    prepared by a method similar to 2s using 1e.                                   ##STR65##                                                                    2,6-bis(4-carboxyphenyl)pyrido[2,3-d:6,5-d']bisoxazole                        prepared by a method similar to 2s using 1f.                                   ##STR66##                                                                    2,6-bis(4-carboxyphenyl)pyrido[2,3-d:5,6-d']bisthiazole                       prepared by a method similar to 2s using 1g.                                   ##STR67##                                                                    1,7-diphenyl-2,6-bis(4-carboxyphenyl)benzobisimidazole                        prepared by a method similar to 2s using 1h.                                   ##STR68##                                                                    oxamide obtained from Aldrich Chemical Co.                                    __________________________________________________________________________

The preferred (2,2) monomers are those wherein Y² comprise twosix-membered rings attached by a covalent carbon-carbon bond each withvalences on the 4-position or each with valences on the 3-position, suchas 4,4'-biphenyl or 3,3'-biphenyl, or Y² comprise two fused six-memberedrings with valence positions being on carbon atoms and having a 1,5relationship to each other, such as 2,6-naphthalene or 2,6-quinoline, orY² is a cycloaliphatic divalent moiety with valences on carbon atoms andin a 1,2-trans configuration, or Y² is a variety of condensed aromaticand heteroaromatic ring systems attached only by carbon-carbon bonds andhaving 2 valences, Z₁ and Z₂ are the same as defined above.

Specific examples of (2,2) monomers preferred for use in the inventioninclude those monomers in Table 5 below.

                  TABLE 5                                                         ______________________________________                                        Monomers of Type 2, Class 2                                                   ______________________________________                                         ##STR69##                                                                    4,4'-biphenyldicarboxylic acid                                                obtained from Aldrich Chemical Co.                                             ##STR70##                                                                    4,4'-biphenyldicarboxylic acid chloride                                       prepared from 2aa.                                                             ##STR71##                                                                    2,6-naphthalenedicarboxylic acid                                              prepared according to the method of B. Raecke and                             H. Schirp, Org. Syn. Coll. Vol. V, page 813                                   (1973) from commercially available 1,8-                                       naphthalenedicarboxylic anhydride.                                             ##STR72##                                                                    2,6-naphthalenedicarboxylic acid chloride                                     prepared from 2cc by treatment with thionyl                                   chloride.                                                                      ##STR73##                                                                    2,6-quinolinedicarboxylic acid                                                prepared from commercially available (Aldrich)                                2,6-dimethyl quinoline by oxidation.                                           ##STR74##                                                                    3,3'-biphenyldicarboxylic acid                                                prepared from o-nitrobenzoic acid by the method                               of M. Kurihara and N. Yoda, J. Macromol. Sci.                                 Chem Al (6), page 1069 (1967).                                                 ##STR75##                                                                    trans-1,2-cyclohexanedicarboxylic acid                                        was obtained from Aldrich Chemical Co. and                                    recrystallized from methanol before use.                                       ##STR76##                                                                    1,4-bis(5-carboxybenzoxazole-2-yl)benzene                                     prepared by the method of J. Preston, W. De                                   Winter and W. L. Hofferbert, J. Heterocyclic                                  Chem. 5, page 269 (1968).                                                      ##STR77##                                                                    1,4-bis(6-carboxybenzothiazole-2-yl)benzene                                   prepared by methods analogous to 2hh.                                          ##STR78##                                                                    2,5-bis(6-carboxybenzothiazole-2-yl)pyridine.                                 prepared by methods analogous to 2hh.                                         ______________________________________                                    

The preferred (2,3) monomers are those wherein Y² may be any aromatic,heteroaromatic and aliphatic divalent species not previously described.

Specific examples of (2,3) monomers preferred for use in the inventioninclude those monomers in Table 6 below.

                  TABLE 6                                                         ______________________________________                                        Monomers of Type 2, Class 3                                                   ______________________________________                                         ##STR79##                                                                    4,4'-(p-phenylenedioxy)dibenzoyl chloride                                     prepared according to the method of R. C. Evers,                              F. E. Arnold, and T. E. Helminiak Macromolecules,                             14, page 925 (1981).                                                           ##STR80##                                                                    4,4'-(p-phenylenedioxy)dibenzonitrile                                         prepared according to method of T. Takekoshi, J.                              G. Wirth, Dr. Heath, J. E. Kochanowski, J. S.                                 Manello, and M. J. Weber, Polym. Prepr., J. Am.                               Chem. Soc., 20 (1), page 179 (1979).                                           ##STR81##                                                                    4,4'-(m-phenylenedioxy)dibenzoic acid                                         prepared according to method of T. Takekoshi, J.                              G. Wirth, Dr. Heath, J. E. Kochanowski, J. S.                                 Manello, and M. J. Weber, Polym. Prepr., J. Am.                               Chem. Soc., 20 (1), page 179 (1979).                                           ##STR82##                                                                    4,4'-(m-phenylenedioxy)dibenzoyl chloride                                     from 2mm according to method of R.C. Evers, F.                                E. Arnold, and T. E. Helminiak, Macromolecules,                               14, page 925 (1981).                                                           ##STR83##                                                                    4,4'-(m-phenylenedioxy)dibenzonitrile                                         prepared according to the method of R. C. Evers,                              F. E. Arnold, and T.E. Helminiak Macromolecules,                              14, page 925 (1981).                                                           ##STR84##                                                                    3,3'-(m-phenylendioxy)dibenzoyl chloride                                      according to the method of R. C. Evers, F. E.                                 Arnold, and T. E. Helminiak Macromolecules, 14,                               page 925 (1981).                                                               ##STR85##                                                                    3,3'-(p-phenylenedioxy)dibenzonitrile                                         prepared according to the method of R. C. Evers,                              F. E. Arnold, and T. E. Helminiak Macromolecules,                             14, page 925 (1981).                                                           ##STR86##                                                                    4,4'-(o-phenylenedioxy)dibenzonitrile                                         prepared according to the method of R. C. Evers,                              F. E. Arnold, and T. E. Helminiak Macromolecules,                             14, page 925 (1981).                                                           ##STR87##                                                                    isophthalic acid                                                              obtained from Pfaltz and Bauer and recrystallized                             from 90% ethanol.                                                              ##STR88##                                                                    4,4'-dicarboxydiphenyl ether                                                  obatined from Polysciences, Inc.                                               ##STR89##                                                                    3,3'-dicarboxydiphenyl ether                                                  prepared from a coupling of m-cresol and m-                                   bromotoluene followed by oxidation by the method                              of M. Tomita, J. Pharm. Soc., Japan, 57, page                                 391 (1937).                                                                    ##STR90##                                                                    succinic acid obtained from Aldrich Chemical Co.                               ##STR91##                                                                    glutaric acid obtained from Aldrich Chemical Co.                               ##STR92##                                                                    adipic acid obtained from Aldrich Chemical Co.                                 ##STR93##                                                                    pimelic acid obtained from Aldrich Chemical Co.                                ##STR94##                                                                    sebacic acid obtained from Aldrich Chemical Co.                               ______________________________________                                    

Type 3 monomers has the general formula ##STR95## wherein Ar³ is atrivalent aromatic or heteroaromatic moiety, and X₃ is O, S, or N--R(R═H or an organic group).

Formula 3 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention may alsofurther be classified into two groups: Class 1 (3,1) and Class 2 (3,2).The first number of the number pairs denotes the monomer type and thesecond number of the pairs denotes the monomer class.

The preferred (3,1) monomers are those wherein Z₃ is the same as definedfor Z₁, Ar³ is a trivalent aromatic or heteroaromatic moiety with thethree valence positions being on carbon atoms and having therelationship that the valence bond between Z₃ and Ar³ is nearlycollinear with the same valence bond in subsequently condensed monomers,and X₃ is defined as for X₁ in Table 1. X₃ and NH₂ are positioned orthoto each other on Ar³.

Specific examples of (3,1) monomers preferred for use in the inventioninclude the monomer in Table 7 below.

                  TABLE 7                                                         ______________________________________                                        Monomers of Type 3, Class 1                                                   ______________________________________                                         ##STR96##                                                                    2-(4-carboxyphenyl)-5,6-diaminobenzimidazole dihydrochloride                  prepared according to R. F. Kovar and F. E. Arnold,                           J. Polym. Sci. Polym. Chem. Ed., 14, page 2807 (1976).                        ______________________________________                                    

The preferred (3,2) monomers are those wherein Z₃, Ar³, and X₃ aredefined as above. The bonds that are formed in homopolymerization of(3,2) monomers are defined in their spatial relationship having an angleof catenation of about 150° to about 180°.

Specific examples of (3,2) monomers preferred for use in the inventioninclude those monomers (shown as hydrohalides or as monomers) in Table 8below.

                  TABLE 8                                                         ______________________________________                                        Monomers of Type 3, Class 2                                                   ______________________________________                                         ##STR97##                                                                    3-mercapto-4-aminobenzoic acid hydrochloride                                  prepared according to Wolfe, AFOSR Final Technical                            Report, Dec. 15, 1980.                                                         ##STR98##                                                                    3-mercapto-4-aminobenzoic acid                                                prepared as described in Example 5.                                            ##STR99##                                                                    3-hydroxy-4-aminobenzoic acid hydrochloride                                   prepared as described by Y. Imai, K. Uno, and Y.                              Iwakura, Makromol. Chem., 83, 179 (1965).                                      ##STR100##                                                                   3-amin-4-hydroxybenzoic acid hydrochloride                                    prepared as described by K. Auwers and H. Rohrig,                             Chem. Ber., 30, 992 (1897).                                                    ##STR101##                                                                   3,4-diaminobenzoic acid                                                       obtained from Aldrich Chemical Co. and                                        recrystallized from deoxygenated water before                                 use.                                                                           ##STR102##                                                                   N.sup.3 -phenyl-3,4-diaminobenzoic acid                                       prepared from p-aminobenzoic acid by                                          chlorination, oxidation to 3-chloro-4-                                        nitrobenzoic acid, followed by anilation and                                  reduction.                                                                     ##STR103##                                                                   N.sup.4 -phenyl-3,4-diaminobenzoic acid                                       prepared by nitration of commercially available                               (Aldrich) p-chlorobenzoic acid, followed by                                   anilation and reduction.                                                       ##STR104##                                                                   4-carboxy-3'-mercapto-4'-aminobiphenyl                                        prepared by nitration of commercially available                               4-carboxybiphenyl (ICN/K and K) and reduction to                              4-amino-4'-carboxybiphenyl, followed by placement                             of the  -o-mercapto group by methods analogous to                             those described for 3a.                                                        ##STR105##                                                                   4-carboxy-3'-amino-4'-hydroxybiphenyl                                         prepared by the nitration of commercially                                     available (ICN/K and K) 4-carboxybiphenyl,                                    conversion to 4-carboxy-p-phenol by reduction and                             diazotization, followed by acetylation,                                       nitration, hydrolysis, and reduction                                           ##STR106##                                                                   4-carboxy-3',4'-diaminobiphenyl                                               prepared by acetylation of 4-amino-4'-                                        carboxylbiphenyl (see preparation of 3h) followed                             by nitration, hydrolysis, and reduction.                                      ______________________________________                                    

Type 4 monomers have the general formula ##STR107## wherein Z₄, Z₅, Z₆,and Z₇ are the same or different and are chosen from the list ofcarboxylic acid derivatives given for Z₁ in Table 4. Z₄ and Z₅, or Z₆and Z₇, or both sets can also be carboxylic acid anhydride groups. Ar⁴is an aromatic or aromatic heterocyclic moiety having four valencepositions at carbon atoms. Ar⁴ can be a six-member ring with the valencepositions having 1, 2, 4, 5 relationship, or Ar⁴ can be two condensedsix-member rings, such as naphthalene. Z₄ and Z₅ as one set and Z₆ andZ₇ as another set must either be ortho-positioned within each set orbear a 1, 4, 5, 8 relationship to each other. An (imaginary) lineperpendicular to the bond between the valence carbons attached to Z₄ andZ₅ must be collinear with the corresponding (imaginary) line for Z₆ andZ₇.

Formula 4 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention areclassified as Class 1 (4,1). The first number of the number pairsdenotes the monomer type and the second number of the pairs denotes themonomer class.

Specific examples of (4,1) monomers preferred for use in the inventioninclude those monomers in Table 9 below.

                  TABLE 9                                                         ______________________________________                                        Monomers of Type 4, Class 1                                                   ______________________________________                                         ##STR108##                                                                   pyromellitic dianhydride                                                      obtained from Aldrich Chemical Co. and sublimed                               or recrystallized (acetic anhydride) before use.                               ##STR109##                                                                   1,4,5,8-naphthalenetetracarboxylic dianhydride                                obtained from Aldrich Chemical Co.                                            ______________________________________                                    

Type 5 monomers has the general formula ##STR110## wherein Z₈ and Z₉ aredefined as for Z₄ and Z₅ in Table 9, Ar⁵ is as defined as in Table 9,the two amino groups are ortho to each other, and Z₈, Z₉, and the twoamino groups are positioned such that two imaginary lines drawnperpendicular to the bonds between their valence carbons are collinear.

Formula 5 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention areclassified as Class 1 (5,1). The number pair (5,1) has the samesignificance as above.

Specific examples of (5,1) monomers preferred for use in the inventioninclude the monomer in Table 10 below.

                  TABLE 10                                                        ______________________________________                                        Monomers of Type 5, Class 1                                                   ______________________________________                                         ##STR111##                                                                   4,5-diaminonaphthalene-1,8-dicarboxylic anhydride                             prepared from the dinitroderivative by chemical                               reduction according to I. Honda and M. Okazaki,                               J. Soc. Org. Synthetic Chem. (Japan), 7, page 25 (1950).                      ______________________________________                                    

Type 6 monomer has the general formula ##STR112## wherein Ar⁶ representsan aromatic moiety and is a tetrahydroxy fused ring system, Z₁₀, Z₁₁,Z₁₂, Z₁₆ are the same HO atoms bonded to carbon atoms of Ar⁶.

In general, Ar⁶ may comprise a single or a plurality of aromatic ringsin the center of a completely conjugated fused ring system. The centeraromatic ring or rings of the completely conjugated fused ring systemcan be any of those described above, and others.

Formula 6 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention may alsobe further classified into two groups: Class 1 (6,1), and Class 2 (6,2).The number pairs have the same significance as above.

The preferred (6,1) monomers are those wherein Ar⁶ comprise a singlecenter aromatic ring in the center of the fused ring system.

The preferred (6,2) monomers are those wherein Ar⁶ comprise at least twocenter aromatic rings in the center of the fused ring system.

Specific examples of (6,1) and (6,2) preferred for use in the inventioninclude those monomers in Tables 11 and 12 respectively.

                  TABLE 11                                                        ______________________________________                                        Monomers of Type 6, Class 1                                                   ______________________________________                                         ##STR113##                                                                   2,3,7,8-tetrahydroxy-1,4,6,9-tetraazaanthracene prepared from                 condensation of 1,2,4,5-tetraaminobenzene with oxalic acid                    according to H. Tadamus, F. DeSchryver, W. DeWinter, and                      C. S. Marvel, J. Polym. Sci. A-1,4, page 2831 (1966).                         ______________________________________                                    

                  TABLE 12                                                        ______________________________________                                        Monomers of Type 6, Class 2                                                   ______________________________________                                         ##STR114##                                                                   2,2',3,3'-tetrahydroxy-6,6'-biquinoxaline prepared from                       condensation of 3,3'-diaminobenzidine with oxalic acid                        according to method of H. Tadamus, et al.,                                    J. Polym. Sci. A-1, 4, page 2831 (1966).                                      ______________________________________                                    

Type 7 monomer has the general formula ##STR115## wherein Y⁷ representsan aromatic or heteroaromatic moiety and is a fused ring carbon group,the X₇ 's are double bonded to carbon of Y⁷.

Formula 7 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention can beclassified as Class 1 (7,1). The number pair (7,1) has the samesignificance as above.

A specific example of (7,1) preferred for use in the present inventionis 7a in Table 13 below.

                  TABLE 13                                                        ______________________________________                                        Monomers of Type 7, Class 1                                                   ______________________________________                                         ##STR116##                                                                   1,2,6,7-tetraketopyrene                                                       M. Corell, and H. Streck, Ann. 531, page 6 (1937).                            ______________________________________                                    

Type 8 monomer has the general formula ##STR117## wherein Y⁸ is a singlecarbon cyclic moiety, X₁₀ and X₁₁ are HO and O atoms respectively,bonded to carbon atoms of Y⁸.

Formula 8 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the instant invention can beclassified as Class 1 (8,1). The number pair (8,1) has the samesignificance as above.

A specific example of (8,1) preferred for use in the present inventionis 8a in Table 14 below.

                  TABLE 14                                                        ______________________________________                                        Monomers of Type 8, Class 1                                                   ______________________________________                                         ##STR118##                                                                   2,5-dihydroxy-1,4-benzoquinone                                                obtained from Aldrich Chemical Co.                                            ______________________________________                                    

Type 9 monomer has the general formula ##STR119## wherein Ar⁹ representsan aromatic moiety and is a partially fused ring system, Z₁₄ and Z₁₅ areOH atoms, X₄ are selected from the class O, S, and NR; R is H or anorganic group attached to N; NH₂, X₄ H, Z₁₄, and Z₁₅ are bonded tocarbon atoms of Ar⁹ ; NH₂ and X₄ H are positioned ortho; Z₁ arepositioned ortho.

Formula 9 monomers useful in preparing the extended chain polymers andnovel liquid-crystalline compositions of the present invention can beclassified as Class 1 (9,1). The number pair (9,1) has the samesignificance as above.

A specific example of (9,1) preferred for use in the present inventionis 9a in Table 15 below.

                  TABLE 15                                                        ______________________________________                                        Monomers of Type 9, Class 1                                                   ______________________________________                                         ##STR120##                                                                   2,3-dihydroxy-6,7-diaminoquinoxaline dihydrochloride                          prepared from 1,2-diamino-4,5-dinitrobenzene by                               condensation with oxalic acid followed by reduction                           according to R. F. Kovar and F. E. Arnold,                                    J. Polym. Sci., Polym. Chem. Ed., 14, page 2807 (1976).                       ______________________________________                                    

All of the above-cited patents and/or publications of Tables 1-15 arespecifically incorporated herein by reference.

In accordance with the practice of the present invention, the synthesisof the aforementioned formulas I-VIII homopolymers may be illustrated bythe following general reaction system: ##STR121##

Representative examples of suitable homopolymers forming liquidcrystalline homopolymer compositions in accordance with the practice ofthe present invention (provided they fall within the above-definedgeneral formulas I-VIII) include the following polymers. For the sake ofconvenience, polymer formulas are hereinbelow shown in simplifiedrepresentation. As an example, --AI--_(n) is ##STR122##

The structures representing --AI-- are defined in the Appendix. --A--has the structure ##STR123## and --I-- has the structure ##STR124##

Their sequential combination is therefore ##STR125##

All simplified polymer formula representations appearing in thespecification may be readily interpreted by reference to the Appendix.##STR126##

The most preferred extended chain homopolymers in accordance with thepractice of the present invention include ##STR127##

The especially preferred extended chain homopolymers in accordance withthe practice of the present invention include ##STR128##

The preferred extended chain homopolymers in accordance with thepractice of the present invention include ##STR129##

It is helpful to define three P₂ O₅ contents, operative at differentstages of polymerization, that must be controlled in order to optimizethe synthesis procedure of the present invention. We will define theinitial P₂ O₅ content m_(o) as the P₂ O₅ content of the polyphosphoricacid operative during dehydrohalogenation (in step b above and asexplained more fully hereinafter). The initial P₂ O₅ content inaccordance with the practice of the instant invention should be belowabout 83.3%, and may range from between about 83.3% to about 63%;preferably below about 82%, more preferably below about 80%, and mostpreferably below about 76%.

The intermediate P₂ O₅ content is operative at the initiation ofpolycondensation and is calculated so as to give the third (or final) P₂O₅ content f that accounts for polyphosphoric acid hydrolysis by 100% ofthe theoretical water of polycondensation. The final P₂ O₅ content, f,must be above some minimum value if the solution is to maintain itseffectiveness as a reaction medium at the late stages of polymerization.The final P₂ O₅ content should be between about 82% to about 86%,preferably between about 82% to about 84%, and most preferably betweenabout 82% to about 83%.

The various important general process steps for preparing liquidcrystalline polymer compositions of the present invention may includeone or more of the following stages which are considered to be withinthe process parameters described above, These stages are:

Stage One--One or more of a selected first monomers selected from thegroup consisting of (amino-group-containing) monomers 1, 3, 5, or 9 isadded to a specified initial weight in grams (given by a*) of apolyphosphoric acid with a P₂ O₅ content m_(o) according to theempirical equation

    a*={[1-f]([P.sub.y /P.sub.c ]-P.sub.y)-[n.sub.o (18.02)/M.sub.w ]P.sub.y } (1-m.sub.o).sup.-1

where P_(y) is the weight in grams of the theoretical yield of polymer,P_(c) is the weight fraction of polymer in the total weight of the finalliquid crystalline polymer composition (and is chosen to be above thecritical concentration of the polymer necessary for liquid crystallinephase formation in the resulting polymer-polyphosphoric acidcomposition), n_(o) is an integer giving the number of moles ofcondensation by-product per mole of polymer repeating unit. The number18.02 is the molecular weight of the condensation by-product, M_(w) ismolecular weight of the polymer repeating unit, and f is the final P₂ O₅content that must be above a minimum value as defined by this invention.

Stage Two--Once the first monomer(s) are combined with polyphosphoricacid, and protecting groups, if present, released, (optionally,depending on the particular polymer and reaction mechanism chosen) astoichiometric amount of one or more of a selected second monomerselected from the group consisting of 2, 4, 6, 7 or 8 is next added andthe chosen value of f is achieved by adding b* (an intermediate weightin grams of P₂ O₅) to the mixture according to the equation.

    b*=[P.sub.y /P.sub.c ]-P.sub.y -[{n.sub.o (18.02)/M.sub.w }] P.sub.y -a*

Stage Three--The resulting mixture (containing the first monomer(s)and/or the second monomer(s)) is then heated to a temperature suitablefor polycondensation. The reaction temperature may range from about 100°C. to about 210° C., preferrably about 110° C. to about 200° C., morepreferrably about 160° C. to about 190° C., and most preferrably about185° C.

The P₂ O₅ content, m_(o), should be low enough to:

(1) achieve efficient dehydrohalogenation and/or

(2) achieve sufficient monomer loading to achieve desired P_(c) withoutfoaming problem or unusually high bulk viscosity. f should be highenough to:

(2a) maintain a polyphosphoric acid composition that is an effectivereaction medium at late stages of polycondensation.

(2b) provide an effective phosphorylating medium as described in N. Yodaand M. Kurihara, "New Polymers of Aromatic Heterocycles byPolyphosphoric Acid Solution Methods", J. Polymer Science,Macromolecular Reviews, Volume 5, (1971), p. 159 at initial stage ofpolymerization. The subject matter of the paper by Yoda and et. al., isspecifically incorporated herein by reference.

(2c) provide an effective solvent for the polymer at the end ofpolycondensation.

For purpose of illustration, a plot of equation a* is presented in FIG.7 showing regions (shaded dash area) of poor monomer 1a solubility. Inthe case of polymer --AI--_(n), the family of P_(c) curves can beutilized as follows:

1. choose a --AI--_(n) polymer concentration, P_(c), as an example 0.16;

2. select a point on the curve P_(c) =0.16 above the shaded dash areaindicating poor monomer 1a solubility;

3. from that point selected, the weight in grams of PPA (a*) of thecorresponding P₂ O₅ content (m_(o)) that should be added to 92.06 g ofmonomer 1a can be determined;

4. after dehydrochlorination is complete, the amount of monomer 2a to beadded is 62.38 g; and

5. if the final P₂ O₅ content (f) has been chosen to be 82.2%, then theamount of P₂ O₅ to be added (b*) is the difference between the amount ofPPA used in step 3 above and the weight of PPA at the end of the curvefor P_(c) =0.16.

The choice of the optimal m_(o) is dependent on the desired polymerconcentration and the solubility limits of the first monomer. The regionof poor solubility for monomer 1a is shown in FIG. 7. Other monomersexhibit different solubility limits. Solubility rankings of somerepresentative monomers are listed below.

monomers with solubilities greater than 1a;

1f, 1g, 3a, 3b, 3c, and 3d;

monomers with solubilities comparable to 1a:

1d, and 3e;

monomers with solubilities less than 1a:

1b, 1c, 1e, 1i, 1k, 3f, 3g, 3h, 3i, and 3j;

and monomers with solubilities much less than 1a:

1b, 1l, 1m, 1n, 1o, 1p, 5a, and 9a.

Accordingly, it is possible to dehydrohalogenate the selectedhydrohalide (monomers) more rapidly; the foaming problem is alleviatedor eliminated; the solution in PPA of lesser P₂ O₅ content than that ofU.S. Pat. No. 4,225,700 is much less viscous and dehydrohalogenation canbe carried out much more readily. Further, a solution of selectedmonomers in PPA of considerably higher concentration is possible and areaction product containing a much higher concentration of polymer ispossible.

The above-mentioned formulas I, III, V, VII, and VIII homopolymercompositions may be prepared in accordance with the above processparameters by:

(a) mixing a selected first monomer (for example, a selected firstmonomer selected from the group consisting of (1,1), (1,2), or (1,3)with or without oxidation protecting atoms or groups with a preliminarysolvent of phosphoric acid having a relatively low phosphorus pentoxidecontent,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a mixture of the first monomer in the preliminary solvent,

(c) adding a selected second monomer (for example, a second monomerselected from the group consisting of (2,1), (2,2), (2,3), (4,1), (6,1),(6,2), (7,1) or (8,1)) in the resulting mixture of step (b) to provide amixture of the first and second monomer in the preliminary solvent,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (c) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization,

(e) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form a firsthomo-oligomeric product having a preselected intrinsic viscosity or afirst homopolymeric product.

Formulas II, IV, and VI homopolymer compositions may be prepared by:

(a) mixing a selected first monomer (for example, a selected firstmonomer selected from the group consisting of (3,1), (3,2), (5,1), or(9,1)) with or without oxidation protecting atoms or groups with apreliminary solvent of phosphoric acid having a relatively lowphosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a mixture of the first monomer in the preliminary solvent,

(c) then increasing the phosphorus pentoxide content of the mixtureresulting from step (b) to provide a first monomer reaction medium ofgreater phosphorus pentoxide content suitable for polymerization,

(d) causing polymerization of the first monomer at a temperaturesufficient to effect reaction at a rate to form a first homo-oligomericproduct having a preselected intrinsic viscosity or a firsthomopolymeric product.

Copolymeric Compositions and Their Preparation

In accordance with a further aspect of the invention, there is provideda liquid-crystalline composition useful in the preparation of fibers andfilms comprising a polycondensation product consisting essentially of ablend of certain polyphosphoric acids and a high concentration of atleast one high molecular weight extended chain copolymer having thegeneral formulas: ##STR130## wherein Ar¹ represents an aromatic moietyand is XXX as defined above, X₁ and X₂ are the same or different and aresulfur, oxygen, or NR (R being hydrogen or an organic group), thenitrogen atoms and X₁ and X₂ being bonded to aromatic carbon atoms ofAr¹, N and X₁ or X₂ of each hereto ring are disposed ortho to oneanother, and Y² is nil or represents a bivalent organic radical and isXXXI as defined above, a_(i) b_(j) represents the molar proportions ofthe respective different recurring units present in said copolymer,y_(ij) represents an average number of the respective differentsequential recurring units present in said copolymer, n being a positiveinteger; ##STR131## wherein Ar¹ represents an aromatic moiety and is XXXas defined above, X₁ and X₂ are the same or different and are sulfur,oxygen, or NR (R being hydrogen or an organic group), the nitrogen atomsand X₁ and X₂ being bonded to aromatic carbon atoms of Ar¹, N and X₁ orX₂ of each hetero ring are disposed ortho to one another and Y²represents a bivalent organic radical and is XXXI as defined above,a_(i) b_(j) m/m+m' represents the molar proportions of the respectivedifferent recurring units present in said copolymer, y_(ij) representsan average number of the respective different sequential recurring unitspresent in said copolymer, Ar³ represents a different aromatic moietyand is XXII as defined above, the nitrogen atom and X₃ being bonded toaromatic carbon atoms of Ar³, c_(k) m'/m+m' represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(k) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, n beinga positive integer; ##STR132## wherein Ar³ represents an aromatic moietyand is XXII as defined above, X₃ is sulfur, oxygen, or NR (R beinghydrogen or an organic group), the nitrogen atoms and X₃ being bonded toaromatic carbon atoms of Ar³, N and X₃ of each hetero ring are disposedortho to one another, c_(k) represents the molar proportions of therespective different recurring units present in said copolymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said copolymer, n being a positive integer;##STR133## wherein Ar¹ represents an aromatic moiety and is XXXII asdefined above. Ar⁴ represents a different aromatic moiety and is XXIIIas defined above, the nitrogen atoms being bonded to Ar¹ and the carbonatoms being bonded to Ar⁴, a_(i) b_(j) represents the molar proportionsof the respective different recurring units present in said copolymer,y_(ij) represents an average number of the respective differentsequential recurring units present in said copolymer, n being a positiveinteger; ##STR134## wherein Ar⁴ represents a different aromatic moietyand is XXIII as defined above, Ar¹ represents an aromatic moiety and isXXXII as defined above, and Ar⁵ represents an aromatic moiety differentfrom Ar⁴ and Ar¹ and is XXIV as defined above, the carbon atoms beingbonded to Ar⁴ and Ar⁵ and the nitrogen atoms being bonded to Ar¹ andAr⁵, n being a positive integer; c_(k) m'/m+m' represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(k) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, a_(i)b_(j) m/m+m' represents the molar proportions of the respectivedifferent recurring units present in said copolymer, y_(ij) representsan average number of the respective different sequential recurring unitspresent in said copolymer, n being a positive integer; ##STR135##wherein Ar¹ represents an aromatic moiety and is XXX as defined above,Ar⁶ represents a different aromatic moiety and is XXV as defined above,X₁ and X₂ are the same or different and are sulfur, oxygen, or NR (Rbeing hydrogen or an organic group), the NH groups and X₄ and X₁ beingbonded to aromatic carbon atoms of Ar⁶ and Ar¹, NH and X₁ or X₂ of eachhereto ring are disposed ortho to one another, a_(i) b_(j) representsthe molar proportions of the respective different recurring unitspresent in said copolymer, y_(ij) represents an average number of therespective different sequential recurring units present in saidcopolymer, n being a positive integer; ##STR136## wherein Ar¹ representsan aromatic moiety and is XXX as defined above, Ar⁶ represents adifferent aromatic moiety and is XXV as defined above, X₁ and X₂ are thesame or different and are sulfur, oxygen, or NR (R being hydrogen or anorganic group), the NH groups and X₁ and X₂ being bonded to aromaticcarbon atoms of Ar⁶ and Ar¹, NH and X₁ or X₂ of each hereto ring aredisposed ortho to one another, a_(i) b_(j) m/m+m' represents the molarproportions of the respective different recurring units present in saidcopolymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said copolymer, Ar⁹represents an aromatic moiety different from Ar⁶ and Ar¹ and is XXVI asdefined above, X₄ is sulfur, oxygen, or NR (R being hydrogen or anorganic group), the NH groups and X₄ being bonded to aromatic carbonatoms of Ar⁶ and Ar⁹, c_(k) m'/m+m' represents the molar proportions ofthe respective different recurring units present in said copolymer,y_(k) represents an average number of the respective differentsequential recurring units present in said copolymer, n being a positiveinteger; ##STR137## wherein Ar¹ represents an aromatic moiety and isXXXII as defined above, Y⁷ represents an aromatic or heteroaromaticmoiety and is XXVIII as defined above, the nitrogen atoms being bondedto aromatic carbon atoms of Ar¹ and bonded to adjacent carbon atoms ofY⁷, a_(i) b_(j) represents the molar proportions of the respectivedifferent recurring units present in said copolymer, y_(ij) representsan average number of the respective different sequential recurring unitspresent in said copolymer, n being a positive integer.

In accordance with the practice of the present invention, the synthesisof the aforementioned formulas IX-XVIII copolymers may be illustrated bythe following general reaction system: ##STR138##

The above-mentioned formulas IX, X, XII, XV, XVI, XVII, and XVIIIcopolymer compositions can be prepared in accordance with the aboveprocess parameters by:

(a) mixing at least two of a selected first monomers (for example, twoor more of a monomer selected from the group consisting of (1,1), (1,2),(1,3), (3,1), (3,2), (5,1), or (9,1)) with or without oxidationprotecting atoms or groups with a preliminary solvent of phosphoric acidhaving a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a mixture of the first monomer in the preliminary solvent,

(c) adding at least one of a selected second monomers (for example, oneor more of a monomer selected from the group consisting of (2,1), (2,2),(2,3), (4,1), (6,1), (6,2), (7,1) or (8,1)) in the resulting mixture ofstep (b) to provide a mixture of the first and second monomer in thepreliminary solvent,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (c) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization,

(e) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form a firstco-oligomeric product having a preselected intrinsic viscosity or afirst copolymeric product.

Similarly formulas IX, XII, XVI, and XVIII copolymer compositions can beprepared by:

(a) mixing at least one of a selected first monomers (for example, oneor more of a monomer selected from the group consisting of (1,1), (1,2),(1,3), (3,1), (3,2), (5,1), or (9,1)) with or without oxidationprotecting atoms or groups with a preliminary solvent of phosphoric acidhaving a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a mixture of the first monomer in the preliminary solvent,

(c) adding at least two of a selected second monomers (for example, oneor more of a monomer selected from the group consisting of (2,1), (2,2),(2,3), (4,1), (6,1), (6,2), (7,1) or (8,1)) in the resulting mixture ofstep (b) to provide a mixture of the first and second monomer in thepreliminary solvent,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (c) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization,

(e) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form a firstco-oligomeric product having a preselected intrinsic viscosity or afirst copolymeric product.

Preferred formulas IX, X, XI, XII, XV, XVI, XVII, and XVIII copolymersforming liquid crystalline copolymer compositions of the instantinvention are those wherein a_(i) is the mole fraction of the ithmonomer selected from Type 1, b_(j) is the mole fraction of the jthmonomer selected from Types 2, 4, 6, 7, or 8, c_(k) is the mole fractionof the kth monomer selected from Types 3, 5, or 9, m and m' areappropriate molar quantities based on desired yield, a_(i) b_(j) anda_(i) b_(j) m/m+m' are the molar proportions of the recurring unitsresulting from the condensation of the ith monomer of Type 1 and the jthmonomer of Type 2, 4, 8, 7, or 8, c_(k) and c_(k) m'/m+m' are the molarproportions of the recurring unit resulting from the condensation of thekth monomer of Type 3, 5, or 9, y_(ij) is the average block length(i.e., the average number of sequential recurring units unbroken by adifferent recurring unit) of the recurring unit formed from the ithmonomer of Type 1 and the jth monomer of Type 2, 4, 6, 7, or 8, y_(k) isthe average block length of the recurring unit formed byself-condensation of the kth monomer of Type 3, 5, or 9, and n is theaverage overall length of the copolymer (i.e., the average total numberof recurring units independent of structure). The number of recurringunits in the copolymer may be the product of the highest i and thehighest j or may be the product of the highest i and the highest j plusthe highest k, i, j and k can be as high as is practical, but may havecertain minimal values if copolymers, rather than homopolymers, are tobe obtained.

Selected molar quantities (a₁ m, a₂ m, . . . , a_(i) m) of monomers ofType 1 may be mixed with a phosphoric acid having a phosphorus pentoxidecontent of from about 63% to about 78%, preferably greater than about68%, most preferably about 78%, and the protecting groups, such ashydrogen halide, if present, may be substantially removed by heating,and applying reduced pressure if desired. The quantity of the phosphoricacid is most desirably determined in accordance with equation a* above,making the necessary calculations for addition of monomers of possiblydifferent molecular weights and different proportions. A stoichiometricquantity (i.e., b₁ m+b₂ m+ . . . b_(j) m=m) of monomer selected fromType 2, 4, 6, 7, or 8 may then be added to the resulting solution. Thephosphorus pentoxide content of the resulting mixture may then be raisedin accordance with equation b* above, so as to raise the finalphosphorus pentoxide content of the substantially copolymerized mixtureto a value preferably within the range between about 81% to about 84%and most preferably between about 82% to about 83.5%. The resultingmixture may then be heated to a temperature preferably about 100° C. toabout 210° C., most preferably to about 170° C. to about 185° C. withina practical time period, from less than about one hour to greater thanabout 5 hours, preferably within about 1 to about 3 hours. Thetemperature may be maintained for a sufficient time, which may rangefrom less than about 1 hour to about 48 hours or more, most preferablybetween from about 1 to about 23 hours, to achieve the desired n value.The practice of the present invention as it relates to the production ofnovel liquid-crystalline compositions comprising copolymers with thegeneral formulas IX, XII, XVI, and XVIII is illustrated for thosecompositions including general formula IX wherein the selected monomersof Type 1 are further classified as being of Types (1,1), (1,2) or (1,3)and the selected monomers of Type 2 are of Types (2,1), (2,2), or (2,3).

General formula IX copolymers prepared from Type (1,1) and Type (2,1)monomers have the advantage that the critical concentration necessaryfor liquid-crystalline behavior is low. For the copolymers listed below,their critical concentration may be as low as about 5 weight percent inpolyphosphoric acid at substantially moderate n values, thus allowing abroad range of operable concentrations. ##STR139##

Since the recurring units of the copolymers are of essentiallycomparable mesogenicity, a broad range of copolymer compositions may beachieved; for instance, a₁ b₁ can range from nearly zero to nearly onewhile a₁ b₂ or a2b₁ (because it is equal to 1-a₁ b₁) ranges from nearlyone to nearly zero, respectively. The average block lengths y₁₁ and y₁₂or y₂₁ are governed by the method of monomer addition described aboveand the molar quantities selected. Thus, for monomer pairs ofessentially equal reactivity. y₁₁, which equals 1/1-a₁ b₁, may rangefrom nearly one to very high values. In a like manner, y₁₂ or y₂₁ canrange from very high values to nearly one. Monomer purity, control ofstoichiometry, and exclusion of side reactions caused by oxidizingimpurities must be sufficient to obtain an overall copolymer length, n,greater than about 50 in order to obtain the desired polymericproperties of useful mechanical strength, modulus, etc. The practice ofthe invention as it relates to copolymers derived from Class 1 monomersis further illustrated in Examples 49-51 and 54-66 below.

General formula IX copolymers may be prepared from type (1,1), (2,1) and(2,2) monomers and from type (1,1), (1,2) and (2,1) monomers. Thesemonomers are classified as Class 2 owing either to a moderately reducedmesogenic character of the recurring unit derived from them or to theirtendency to reduce the solubility range of the resulting polymer, whichin turn is usually owing to an overall reduction of theheteroatom/hydrocarbon ratio of the resulting polymer. Both of theseconditions dictate that incorporation of Class 2 monomers intocopolymers of the present invention should be carefully selected. Thedegree of this selectivity is illustrated by the following copolymersprepared in accordance with the practice of the invention. ##STR140##

The immediately preceding list of copolymers is derived from monomercompositions containing monomers imparting reduced solubility to thecopolymer. The preferred values of a₁ b₁ (i.e., the mole fraction of themore soluble recurring unit) are those greater than about 0.8, leadingto values of y₁₁ greater than about 5 and y₁₂ values of nearly one.Monomer purity, control of stoichiometry, exclusion of oxidizingimpurities, and selection of the molar quantity of the less solublemonomer to maintain copolymer solubility must be sufficient to achievean average n value of greater than about 50. Increased proportion of aless soluble monomer may be achieved by selecting comonomers that impartimproved solubility to the copolymer. In general, monomers of Type 1wherein X is S impart greater solubility than those in which X is O orN. The practice of the invention as it relates to copolymers ofpartially reduced solubility is further illustrated in Examples 52, 53,70, 71, and 72 below.

The following list of copolymers is derived from incorporation ofmonomers of moderately reduced mesogenicity and the practice of theinvention is illustrated for them. ##STR141##

The preferred ranges of a₁ b₁ are from nearly zero to nearly one forcopolymers in this classification with the overall proviso that theoverall copolymer concentration in the polyphosphoric acid be above acritical concentration determined by the least mesogenic recurring unit.Thus, above about 13% the above copolymers may have a₁ b₁ values betweenabout one and zero, y₁₁ values of nearly one and greater, and y₂₁ valuesof nearly one and greater. The preferred concentration with these a₁ b₂and a₂ b₁ values may be between about 15 and about 22 weight percent. Ifthe molar proportion of the more highly mesogenic recurring unit (i.e.,a₁ b₁) is selected to have values of greater than about 0.6, preferablygreater than about 0.75, then the range of operable concentrations isincreased to include concentrations of the copolymer in greater thanabout 8 weight percent, preferably above about 10 weight percent. Valuesof n greater than about 50 are preferable as stated above.

General formula IX copolymer compositions may be prepared from Class 3monomers.

Monomers characterized as belonging to Class 3 lead to polymer recurringunits that have little or no mesogenic character. Their incorporationinto copolymers prepared as above are within the scope of the presentinvention but are less preferred because the random incorporation of asignificant molar proportion of these non-mesogenic units leads toinsufficient block length of the mesogenic recurring unit or units toimpart liquid-crystalline behavior. Incorporation of less than about 3molar percent of Class 3 monomers is preferred. Increased incorporationof Class 3 polymers are highly preferred by use of a block polymerprocedure described below. A less preferred embodiment of the presentinvention is the preparation of General formulas X, XV, and XVII by theaddition of monomers of Types 3, 5, and 9, respectively, to the initialsolution of the above copolymer procedure. The unique feature of thegeometry of monomers of Types 3 (except for 3k), 5, and 9 is therequirement that the block lengths, y_(k), be large or, if small, be aneven number. This condition dictates that preferred compositions offormulas X, XV, and XVII are prepared by a block polymer proceduredescribed below.

The general formula XI copolymer composition shown above is preparedaccording to the following procedure:

(a) mixing at least two of a selected first monomer with or withoutoxidation protecting atoms or groups with a preliminary solvent ofphosphoric acid having a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a mixture of the first monomer in the preliminary solvent,

(c) then increasing the phosphorus pentoxide content of the mixtureresulting from step (b) to provide a first monomer reaction medium ofgreater phosphorus pentoxide content suitable for polymerization,

(d) causing polymerization of the the first and second monomer at atemperature sufficient to effect reaction at a rate to form a firstco-oligomeric product having a preselected intrinsic viscosity or afirst copolymeric product.

Selected molar quantities (c₁ m, c₂ m, . . . , c_(k) m) of Type 3monomers may be mixed with a phosphoric acid having a phosphoruspentoxide content of from about 63% to about 78%, preferably greaterthan about 68%, most preferably about 78%, and the protecting groups, ifpresent, may be substantially removed by heating, and applying reducedpressure, if desired. The quantity of phosphoric acid is determined inaccordance with equation a* above, making the necessary calculations forthe addition of monomers of possibly different molecular weights anddifferent proportions. The phosphorus pentoxide content of the resultingmixture may then be raised in accordance with equation b* above, so asto raise the final phosphorus pentoxide of the substantiallycopolymerized mixture to a value greater than about 81%, most preferablybetween about 82% to about 83% but less than about 84%. The resultingmixture may then be heated to about 100° C. to about 200° C., mostpreferably between about 150° C. to about 185° C. within a practicalperiod of time, preferably within a time period of less than about 1hour to about 5 hours or more, and most preferably within a period ofabout 1 hour to about 3 hours, and then maintained at the selectedtemperature for sufficient time to achieve the desired n value.

The practice of the present invention as it relates to the production ofnovel liquid-crystalline compositions that include copolymers with thegeneral formula XI is further illustrated for those compositions whereinthe selected monomers of Type 3 are further classified as being of Type(3,2).

The polymers ##STR142## are prepared according to the above procedurewherein c₁ is the molar proportion of the more soluble recurring unitand selected to be above about 0.5, more preferably above about 0.7, toensure the solubility of the resulting copolymer to the highconcentrations required for liquid-crystalline behavior. A weightpercent of the copolymer above about 15 weight percent, more preferablyabove about 17.5 weight percent, may be selected. Molar proportionsselected above and monomer reactivity ratios determine the average blocklengths y₁ and y₂. The block length does not bear on whetherliquid-crystalline behavior in polyphosphoric acid is obtained withthese polymers. The important factor is the maintenance of solubility athigh concentration and the preparation of these copolymers inpolyphosphoric acid at high concentration from monomers.

Blockpolymeric Compositions and Their Preparation

In accordance with a still further aspect of the invention, there isprovided a liquid-crystalline composition useful in the preparation offibers and films comprising a polycondensation product consistingessentially of a blend of certain polyphosphoric acids and a highconcentration of at least one high molecular weight extended chain blockpolymer having the general formulas: ##STR143## wherein Ar¹ representsan aromatic moiety and is XXX as defined above, X₁ and X₂ are the sameor different and are sulfur, oxygen, or NR (R being hydrogen or anorganic group), the nitrogen atoms and X₁ and X₂ being bonded toaromatic carbon atoms of Ar¹, N and X₁ or X₂ of each hereto ring aredisposed ortho to one another and Y² is nil or represents a bivalentorganic radical and is XXXI as defined above, a_(i) b_(j) represents themolar proportions of the respective different recurring units present insaid block polymer, y_(ij) represents an average number of therespective different sequential recurring units present in said blockpolymer, n being a positive integer; ##STR144## wherein Ar¹ representsan aromatic moiety and is XXX as defined above, X₁ and X₂ are the sameor different and are sulfur, oxygen, or NR (R being hydrogen or anorganic group), the nitrogen atoms and X₁ and X₂ being bonded toaromatic carbon atoms of Ar¹, N and X₁ or X₂ of each hetero ring aredisposed ortho to one another and Y² is nil or represents a bivalentorganic radical and is XXXI as defined above, a_(i) b_(j) m/m+m'represents the molar proportions of the respective different recurringunits present in said block polymer, y_(ij) represents an average numberof the respective different sequential recurring units present in saidblock polymer, Ar³ represents an aromatic moiety and is XXII as definedabove, X₃ is sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the nitrogen atoms and X₃ being bonded to aromatic carbon atomsof Ar¹, N and X₃ of each hetero ring are disposed ortho to one another,c_(k) m'/m+m' represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said block polymer, n being a positiveinteger; ##STR145## wherein Ar³ represents an aromatic moiety and isXXII as defined above, X₃ is sulfur, oxygen, or NR (R being hydrogen oran organic group), the nitrogen atoms and X₃ being bonded to aromaticcarbon atoms of Ar³, N and X₃ of each hetero ring are disposed ortho toone another, c_(k) represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said block polymer, n being a positiveinteger; ##STR146## wherein Ar¹ represents an aromatic moiety and isXXXII as defined above, Ar⁴ represents a different aromatic moiety andis XXIII as defined above, the nitrogen atoms being bonded to Ar¹ andthe carbon atoms being bonded to Ar⁴, a_(i) b_(j) represents the molarproportions of the respective different recurring units present in saidblock polymer, y_(ij) represents sa average number of the respectivedifferent sequential recurring units present in said block polymer, nbeing a positive integer; ##STR147## wherein Ar¹ represents an aromaticmoiety and is XXXII or XXX as defined above with the proviso that whenAr¹ is bonded to nitrogen toms Ar¹ is XXXII and when Ar¹ is bonded toboth nitrogen atoms and X₁ and X₂, Ar¹ is XXX as defined above, Ar⁴represents a different aromatic moiety and is XXIII as defined above,the carbon atoms being bonded to Ar⁴, m'/m+m' represents the molarproportions of the respective different recurring units present in saidblock polymer, y' represents an average number of the respectivedifferent sequential recurring units present in said block polymer, X₁and X₂ are the same or different and are sulfur, oxygen, or NR (R beinghydrogen or an organic group), the nitrogen atoms and X₁ and X₂ beingbonded to aromatic carbon atoms of Ar⁴, N and X₁ or X₂ of each heretoring are disposed ortho to one another and Y² is nil or represents abivalent organic radical and is XXXI as defined above, m/m+m' representsthe molar proportions of the respective different recurring unitspresent in said block polymer, y represents an average number of therespective different sequential recurring units present in said blockpolymer, n being a positive integer; ##STR148## wherein Ar³ representsan aromatic moiety and is XXII as defined above, X₃ is sulfur, oxygen,or NR (R being hydrogen or an organic group), the nitrogen atoms and X₃being bonded to aromatic carbon atoms of Ar³, N and X₃ of each heteroring are disposed ortho to one another, p represents the molarproportions of the respective different recurring units present in saidblock polymer, y'/2 represents an average number of the respectivedifferent sequential recurring units present in said block polymer, Ar¹represents an aromatic moiety and is XXXII as defined above, Ar⁴represents a different aromatic moiety and is XXIII as defined above,the nitrogen atoms being bonded to Ar¹ and the carbon atoms being bondedto Ar⁴, q represents the molar proportions of the respective differentrecurring units present in said block polymer, y represents an averagenumber of the respective different sequential recurring units present insaid block polymer, n being a positive integer; ##STR149## wherein Ar⁴represents a different aromatic moiety and is XXIII as defined above,Ar¹ represents an aromatic moiety and is XXXII as defined above, and Ar⁵represents an aromatic moiety different from Ar⁴ and Ar¹ and is XXIV asdefined above, the carbon atoms being bonded to Ar⁴ and Ar⁵ and thenitrogen atoms being bonded to Ar¹ and Ar⁵, n being a positive integer;c_(k) m'/m+m' represents the molar proportions of the respectivedifferent recurring units present in said block polymer, y_(k)represents an average number of the respective different sequentialrecurring units present in said block polymer, a_(i) b_(j) m/m+m'represents the molar proportions of the respective different recurringunits present in said block polymer, y_(ij) represents an average numberat the respective different sequential recurring units present in saidblock polymer, n being a positive integer; ##STR150## wherein Ar¹represents an aromatic moiety and is XXX as defined above, Ar⁶represents a different aromatic moiety and is XXV as defined above, X₁and X₂ are the same or different and are sulfur, oxygen, or NR (R beinghydrogen or an organic group), the NH groups and X₁ and X₂ being bondedto aromatic carbon atoms of Ar⁶ and Ar¹, NH and X₁ or X₂ of each heteroring are disposed ortho to one another, a_(i) b_(j) represents the molarproportions of the respective different recurring units present in saidblock polymer, y_(ij) represents an average number of the respectivedifferent sequential recurring units present in said block polymer, nbeing a positive integer; ##STR151## wherein Ar¹ represents an aromaticmoiety and is XXX as defined above, Ar⁶ represents a different aromaticmoiety and is XXV as defined above, X₁ and X₂ are the same or differentand are sulfur, oxygen, or NR (R being hydrogen or an organic group),the NH groups and X₁ and X₂ being bonded to aromatic carbon atoms of Ar⁶and Ar¹, NH and X₁ or X₂ of each hetero ring are disposed ortho to oneanother, a_(i) b_(j) m/m+m' represents the molar proportions of therespective different recurring units present in said block polymer,y_(ij) represents an average number of the respective differentsequential recurring units present in said block polymer, Ar⁹ representsan aromatic moiety different from Ar⁶ and Ar¹ and is XXVI as definedabove, X₄ is sulfur, oxygen, or NR (R being hydrogen or an organicgroup), the NH groups and X₄ being bonded to aromatic carbon atoms ofAr⁶ and Ar⁹, c_(k) m"/m+m' represents the molar proportions of therespective different recurring units present in said block polymer,y_(k) represents an average number of the respective differentsequential recurring units present in said block polymer, n being apositive integer; ##STR152## wherein Ar¹ represents an aromatic moietyand is XXXII as defined above, Y⁷ represents an aromatic orheteroaromatic moiety and is XXVIII as defined above, the nitrogen atomsbeing bonded to aromatic carbon atoms of Ar¹ and bonded to adjacentcarbon atoms of Y⁷, a_(i) b_(j) represents the molar proportions of therespective different recurring units present in said block polymer,y_(ij) represents an average number of the respective differentsequential recurring units present in said block polymer, n being apositive integer.

In accordance with the practice of the present invention, the synthesisof the aforementioned formulas IX-XIX block polymers can be illustratedby the following general reaction system: ##STR153##

The above-mentioned formulas IX, XII, XVI, XVIII, and XIX block polymercompositions may be prepared in accordance with the above processparameters by:

(a) mixing at least one of a selected first monomer with or withoutoxidation protecting atoms or groups with a preliminary solvent ofphosphoric acid having a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a mixture of the first monomer in the preliminary solvent,

(c) adding at least one of a selected second monomer in the resultingmixture of step (b) to provide a mixture of the first and second monomerin the preliminary solvent,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (c) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization,

(e) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form a firsthomo-oligomeric product having a preselected intrinsic viscosity,

(f) mixing a selected amount of the first homo-oligomeric product with aselected amount of at least one of a selected second homo-oligomericproduct so as to form a first poly-oligomeric product, said secondhomo-oligomeric product being formed by like steps (a), (b), (c), (d),and (e) with the overall proviso that at least one of the selectedmonomer of step (a) or (c) which forms the second homo-oligomericproduct be different from at least one of the selected monomer of step(a) or (c) which forms the first homo-oligomeric product,

(g) causing polymerization of the poly-oligomeric product at atemperature sufficient to effect reaction at a rate to form a firstblock-oligomeric product having a preselected intrinsic viscosity or afirst block-polymeric product.

Alternatively, formulas IX, XII, XVI, XVIII, and XIX block polymercompositions may be prepared by:

(a) mixing at least one of a selected first monomer with or withoutoxidation protecting atoms or groups with a preliminary solvent ofphosphoric acid having a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a mixture of the first monomer in the preliminary solvent,

(c) adding at least one of a selected second monomer in the resultingmixture of step (b) to provide a first mixture of the first and secondmonomer in the preliminary solvent,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (c) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization,

(e) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form a firsthomo-oligomeric product having a preselected intrinsic viscosity,

(f) mixing a selected amount of the first homo-oligomeric product with aselected amount of a second mixture of a different first and secondmonomer in the preliminary solvent, said second mixture being formed bylike steps (a), (b) and (c) with the overall proviso that at least oneof the selected monomer of step (a) or (c) which forms the secondmixture be different from at least one of the selected monomer of step(a) or (c) which forms the first homo-oligomeric product,

(g) then increasing the phosphorus pentoxide content of the mixtureresulting from step (f) to provide a first oligomer-monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization,

(h) causing polymerization of the mixture resulting from step (g) at atemperature sufficient to effect reaction at a rate to form a firstblock-oligomeric product having a preselected intrinsic viscosity or afirst block-polymeric product.

The above IX-XIX block polymers forming the liquid crystalline blockpolymer compositions of the instant invention can be characterized ashaving more than one recurring unit, the distribution or sequencing ofwhich may be different from that obtained by the random condensation ofmonomers as in the copolymers described above and is furthercharacterized as having contiguous blocks of the same recurring unit asobtained by the random condensation of oligomers.

The preferred formulas IX, XII, XVI, XVIII, and XIX block polymers arethose polymers wherein a_(i) b_(j) is the mole fraction of the recurringunit formed by the condensation of a homo-oligomeric reaction product(defined below) derived from the ith monomer of Type 1 with astoichiometric quantity of jth monomer of Type 2, 4, 6, 7, or 8,respectively, and incorporated by a block-polymeric procedure describedbelow, and y_(ij) and n have the same meaning as described above forcopolymers.

The preferred XI block polymers are those wherein c_(k) is the molefraction of the recurring unit formed by the condensation of ahomo-oligomeric reaction product (defined below) derived from the kthmonomer of Type 3 and incorporated by a block polymeric proceduredescribed below, and y_(k) and n are as defined for copolymers.

The preferred X, XV, and XVII block polymers are those wherein a_(i)b_(j) m/m+m' is the mole fraction of the recurring unit formed by thecondensation of m moles of recurring units of a homo-oligomeric reactionproduct derived from the ith monomer of Type 1 and the jth monomer ofType 2, 4, or 6 and combined with m' moles of recurring units of ahomo-oligomeric reaction product derived from condensation of the kthmonomer of Type 3, 5, or 9, respectively, and y_(ij), y_(k), and n areas defined for copolymers.

The preferred XIII block polymers are those wherein m' and m areappropriate molar quantities of the monomers that form the reactionproducts and are selected to give desired yields and molar proportionsof the respective recurring units, y' and y are block lengths as definedabove, n is the total number of recurring units, and x is a molarquantity substantially less than m' that is selected to give anappropriate block length of the first homo-oligomer end-capped witho-diamine functional groups,

The preferred XIV block polymers are those wherein m', m, x, n, y, y'are as defined above, q is equal to m'/m+m' and p is equal to m/2(m+m').

Selected molar quantity, m, of a monomer of Type 1 may be mixed with aphosphoric acid having a phosphorus pentoxide content of from about 63%to about 78%, preferably greater than about 68%, most preferably about78%, and the protecting groups, if present, may be removed as describedpreviously. The quantity of the phosphoric acid is most desirablydetermined in accordance with equation a* as described above. Astoichiometric quantity (i.e., m) of a monomer of Type 2, 4, 6, 7, or 8may then be added to the resulting solution. The phosphorus pentoxidecontent of the resulting mixture may then be raised in accordance withequation b* given above, so as to raise the final phosphorus pentoxidecontent of the substantially polymerized mixture to a value greater thanabout 81%, most preferably between about 82% to about 83.5%, but lessthan about 84%. The resulting mixture may then be heated to about 100°C. to about 185° C., most preferably to about 170° C. to about 185° C.,within a practical period of time, preferably within a period of fromless than about one to about 5 hours, most preferably from about one toabout 3 hours. This temperature is maintained for sufficient time toachieve a selected n value, hereinafter referred to as thehomo-oligomeric n value, that is above a selected minimum value to bedescribed for specific cases below, is characterized as being equal to1/2(1-p), where p is the extent of reaction, defined as the molefraction of either type of functional group present that has undergonecondensation, and being preferrably below a selected maximum valuecharacteristic of complete polymerization. A selected molar quantity,m_(ij), of the homo-oligomeric reaction product thus obtained isdiverted into a second vessel containing a selected molar quantity,m_(ij), of a similarly obtained but structurally differenthomo-oligomeric reaction product and the heating at elevatedtemperatures continued.

The average block lengths, y_(ij), of the block polymers may bedetermined the following way. The ijth oligomeric reaction product isprepared by adding a_(i) moles of a first monomer to an equimolar amountb_(j) of the second monomer. The sum of all a_(i) or b_(j) is 1. Themixture is polymerized to a selected intermediate extent of reaction,p_(ij). The oligomeric n value of the ijth oligomeric reaction product,n_(ij), is given by 1/2(1-p_(ij)). The molar proportions of therecurring units incorporated into the block polymer are given by##EQU5##

The block lengths y_(ij) can be calculated by the equation ##EQU6##which assumes that the homo-oligomers condense with equal reactivity.The above equation for y_(ij) shows that if either of twohomo-oligomeric reaction products are polymerized to high conversion,(i.e., allowed to achieve a high n_(ij) value before mixing) then bothblock lengths in the resulting block polymer will be high.

The practice of the present invention as it relates to the production ofnovel liquid-crystalline compositions that include block polymers withthe general formulas IX, XII, XVI, XVIII, and XIX is illustrated forthose compositions including general formula IX wherein the selectedfirst homo-oligomer may be prepared from monomers of Type 1 and Type 2that are further classified as belonging to Class 1 and the selectedsecond homo-oligomer is further characterized as belonging to eitherClass 1, Class 2, or Class 3.

General formula IX block polymers may be prepared from homo-oligomersderived exclusively from Class 1 monomers. The block polymers,##STR154## have the same advantage of a broad range of operableconcentrations as described for copolymers formed exclusively from Class1 monomers. The advantage to the block polymer procedure described abovefor these polymers is the ability to vary y₁₁ and y₁₂, or y₂₁, or y₂₂essentially independent of the molar proportion a₁ b₁, or a₂ b₂, or a₂b₁, or a₁ b₂ by selecting appropriate extents of reaction for thecorresponding homo-oligomer. For example, y₁₁ may be 20 or greater for abroad range of a₁ b₁ values by increasing the extent of reaction, p₁₁,as the a₁ b₁ value is decreased, y₁₂, y₂₁, or y₂₂ of the above formulasmay be obtained with values from about one to about 75, most preferablyfrom about 25 to about 50, by selecting appropriate p₁₁ and p₁₂, p₂₁, orp₂₂ values. In practice, the members of this selected class of blockpolymers, because all the recurring units have a high degree ofmesogenicity, are liquid-crystalline when an n value of greater thanabout 40 is obtained at a concentration of greater than about 6 weightpercent independent of the block lengths achieved. The practice of theinvention as it relates to block polymers of Class 1 is furtherillustrated in Examples 75-84 below.

General formula IX block polymers may be prepared from a firsthomo-oligomer of Class 1 and a second homo-oligomer derived from monomerpairs containing Class 2 monomers. The block polymers, ##STR155## arederived from homo-oligomers of different mesogenicity. The selection ofa₁ b₁ (the molar proportion of the first and more highly mesogenicrecurring unit) and the preferred y₁₁ (the average block length of thefirst and more highly mesogenic recurring unit) are governed by thefollowing considerations. The block polymer reaction product in thefirst case may derive liquid-crystalline behavior by virtue of the solepresence of the first recurring unit when y₁₁ is greater than about 30,more preferably greater than about 40, at concentrations of the firstrecurring unit alone (i.e., the weight of the first oligomeradded/weight of the final block polymer reaction product) greater thanabout 7 percent, or the block polymer reaction product in the secondcase may derive liquid-crystalline behavior by virtue of the combinedpresence of both recurring units, independent of y₁₁, at concentrationsabove which the moderately mesogenic recurring unit derived from thesecond homo-oligomer is liquid-crystalline alone. The preferred valuesof a₁ b₁ are from about 0.4 to about one, with y₁₁ ranging from about 80to about 20, respectively, as a₁ b₁ is varied from 0.4 to one. The mostpreferred concentrations of these block polymers is above about 15weight percent but may be lower as either the a₁ b₁ value or the y₁₁value or both values are increased. The preferred n value for thesecompositions is from about 50 to 150, most preferably greater than 100.Obtaining sufficient n values may be aided by the addition of the secondhomo-oligomeric reaction product before the phosphorus pentoxide contentis raised to the value necessary for polymerization (i.e., when p₁₂ orp₂₁ is zero and n₁₂ or n₂₁ =1/2) and then adding the appropriate amountof phosphorus pentoxide to raise the mixture to sufficient phosphoruspentoxide content. This procedure aids in mixing and is most preferredwhen the homo-oligomeric n value of the first homo-oligomer, n₁₁, islarge. The practice of the invention as it relates to the preparation ofblock polymers of Class 2 is further illustrated in Examples 85-88below.

General formula IX block polymers may be prepared from a firsthomo-oligomer of Class 1 and a second homo-oligomer derived from monomerpairs containing Class 3 monomers. The block polymers ##STR156## derivetheir liquid-crystalline behavior entirely from the presence of thefirst recurring unit, its average block length y₁₁, and itsconcentration alone in the total weight of the final block polymerreaction product. Thus, the values of a₁ b₁, y₁₁, and concentration mustmeet the conditions of the first case described for the block polymerscontaining Class 2 monomers. The method of the invention allows thepreparation of such highly concentrated mixtures of mesogenic units,i.e., reaction products substantially higher in polymer concentrationthan that required for liquid-crystalline behavior, that incorporationof significant amounts of non-mesogenic units is possible if the aboveconditions are met.

The preferred values of a₁ b₁ are from about 0.6 to about one. Thepreferred values of y₁₁ are from at least about 30 to about 100, morepreferably between about 50 to 100. The preferred values of y₁₂ or y₂₁are from about one to about 50. The preferred values of n are from about50 to 200 with the most preferred values being about 100 to 150. Thepreferred selected concentrations of the block polymer are above about15 weight percent, especially as the proportion of the non-mesogenicrecurring unit is increased. The practice of the invention as it relatesto production of block polymers containing Class 3 monomers is furtherillustrated in Examples 73, 74, 89-94 below.

The practice of the invention as it relates to the production of novelliquid-crystalline compositions that include block polymers with thegeneral formulas X, XV, XVII are illustrated for block polymers offormula X wherein the selected first homo-oligomer is prepared from Type(1,1) or (1,2) and Type (2,1) monomers and the selected secondhomo-oligomer is prepared from monomers of Type (3,2).

The general formulas X, XV, and XVII liquid crystalline block polymercompositions shown above are prepared according to the followingprocedure:

(a) mixing at least one of a selected first monomer with or withoutoxidation protecting atoms or groups with a preliminary solvent ofphosphoric acid having a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a mixture of the first monomer in the preliminary solvent,

(c) then increasing the phosphorus pentoxide content of the mixtureresulting from step (b) to provide a first monomer reaction medium ofgreater phosphorus pentoxide content suitable for polymerization,

(d) causing polymerization of the first monomer at a temperaturesufficient to effect reaction at a rate to form a first homo-oligomericproduct having a preselected intrinsic viscosity,

(e) mixing a selected amount of the first homo-oligomeric product with aselected amount of at least one of a selected second homo-oligomericproduct so as to form a first poly-oligomeric product, said secondhomo-oligomeric product being formed by like steps (a) and (b) followedby:

(1e) adding at least one of a selected second monomer in the resultingmixture of step (b) to provide a mixture of a first and second monomerin the preliminary solvent,

(2e) then increasing the phosphorus pentoxide content of the mixtureresulting from step (1e) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization,

(3e) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form said secondhomo-oligomeric product having a preselected intrinsic viscosity,

with the overall proviso that at least one of the selected monomer ofstep (a) or (1e) which forms the second homo-oligomeric product bedifferent from at least one of the selected monomer of step (a) whichforms the first homo-oligomeric product,

(f) causing polymerization of the poly-oligomeric product at atemperature sufficient to effect reaction at a rate to form a firstblock-oligomeric product having a preselected intrinsic viscosity or afirst block-polymeric product.

Alternatively, the general formulas X, XV, and XVII liquid crystallineblock polymer compositions shown above may be also prepared by:

(a) mixing at least one of a selected first monomer with or withoutoxidation protecting atoms or groups with a preliminary solvent ofphosphoric acid having a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a mixture of the first monomer in the preliminary solvent,

(c) mixing a selected amount of the solution of step (b) with a selectedamount of at least one of a selected first homo-oligomeric product so asto form a first oligomeric-first monomer reaction medium, said firsthomo-oligomeric product being formed by like steps (a) and (b) followedby:

(1c) adding at least one of a selected second monomer in the resultingsolution of step (b) to provide a mixture of a first and second monomerin the preliminary solvent,

(2c) then increasing the phosphorus pentoxide content of the mixtureresulting from step (1) to provide a first and second monomer reactionmedium of greater phosphorus pentoxide content suitable forpolymerization,

(3c) causing polymerization of the first and second monomer at atemperature sufficient to effect reaction at a rate to form said firsthomo-oligomeric product having a preselected intrinsic viscosity,

with the overall proviso that at least one of the selected monomer ofstep (a) or (1c) which forms the first monomer mixture, be differentfrom at least one of the selected monomer of step (a) which forms thefirst homo-oligomeric product,

(d) then increasing the phosphorus pentoxide content of the mixtureresulting from step (c) to provide a reaction medium of greaterphosphorus pentoxide content suitable for polymerization,

(e) causing polymerization of the first oligomer-monomer at atemperature sufficient to effect reaction at a rate to form a firstblock-oligomeric product having a preselected intrinsic viscosity or afirst block-polymeric product.

General formula X block polymers may be derived from a firsthomo-oligomer of Class 1 and a second homo-oligomer of Type (3,2). Theblock polymers of general formula X are prepared by a procedureanalogous to the procedure described for general formula IX blockpolymers, except that the second homo-oligomer is prepared from a singlemonomer.

The polymers ##STR157## have preferred molar proportion of the firstrecurring unit, a₁ b₁ m/m+m' of from about zero to about 0.5 when theconcentration selected to be above about 15 weight percent. When a₁ b₁m/m+m' is selected to be above about 0.5 but less than one then theoperable concentration range is extended to include concentrations of7%, more preferably 10 weight percent. At concentrations above about 15weight percent all selected values of y₁₁ and values of y₁ greater thanabout 5 give liquid-crystalline products, but n must be greater thanabout 50, preferably above about 100 to give desirable mechanicalproperties.

The practice of the invention as it relates to the block polymers ofthis Class is further illustrated in Examples 102-112 below.

General formula X block polymer may be derived from a firsthomo-oligomer of Class 2 and a second homo-oligomer of Type (3,2). Theblock polymers ##STR158## are prepared from two homo-oligomers of Class2 which dictates the selection of concentrations greater than about 15weight percent. The molar proportions of the various recurring units areselected based on desired mechanical properties or the maintenance ofsolubility in two recurring units of different solubilitycharacteristics. The preferred values of y₁ are those from about 5-50,more preferably greater than 30. The practice of the invention as itrelates to block polymers of this Class is further illustrated inExamples 113-115 below.

The practice of the invention is illustrated for general formula XI forblock polymers prepared from a single monomer of Type (3,2).

The general formula XI liquid crystalline block polymer compositionsshown above are prepared according to the following procedure:

(a) mixing at least one of a selected first monomer with or withoutoxidation protecting atoms or groups with a preliminary solvent ofphosphoric acid having a relatively low phosphorus pentoxide content,

(b) heating and optionally placing the resulting mixture under reducedpressure to remove any volatilized protecting atoms or groups presentand provide a mixture of the first monomer in the preliminary solvent,

(c) then increasing the phosphorus pentoxide content of the mixtureresulting from step (b) to provide a first monomer reaction medium ofgreater phosphorus pentoxide content suitable for polymerization,

(d) causing polymerization of the first monomer at a temperaturesufficient to effect reaction at a rate to form a first homo-oligomericproduct having a preselected intrinsic viscosity,

(e) mixing a selected amount of the first homo-oligomeric product with aselected amount of at least one of a selected second homo-oligomericproduct so as to form a first poly-oligomeric product, said secondhomo-oligomeric product being formed by like steps (a), (b), (c), and(d) with the overall proviso that at least one of the selected monomerof step (a) which forms the second homo-oligomeric product be differentfrom at least one of the selected monomer of step (a) which forms thefirst homo-oligomeric product,

(f) causing polymerization of the poly-oligomeric product at atemperature sufficient to effect reaction at a rate to form a firstblock-oligomeric product having a preselected intrinsic viscosity or afirst block-polymeric product.

The block polymers ##STR159## have preferred values of c₁ between 0.5and one, owing to the greater solubility and mesogenicity of the firstrecurring unit and preferred values of y₁ greater than about 25 but lessthan about 100, owing to the higher mesogenicity. Concentrations greaterthan about 15%, more preferably greater than about 18%, and mostpreferably 20%, are selected. Examples 98-101 below further illustratethe method of the present invention.

The method of the invention also relates to the preparation of blockpolymers by the condensation of co-oligomeric reaction products, insteadof the homo-oligomeric reaction products described in the aboveprocedures.

Intrinsic Viscosity

Intrinsic viscosity is determined by extrapolation of η_(rel) -1/c andln η_(rel) /c to zero concentration in methane sulfonic acid at 30° C.

Anisotropic Character of the Compositions

The extended chain polymer compositions of this invention are opticallyanisotropic, i.e., microscopic regions of a given extended chaincomposition are birefringent; a bulk extended chain composition sampledepolarizes plane-polarized light because the light transmissionproperties of the microscopic areas of the extended chain compositionvary with direction. This characteristic is associated with theexistence of at least part of the extended chain polymer compositions inthe liquid crystalline or mesomorphic state.

The extended chain polymer compositions of this invention that exhibitoptical anisotropy do so while the extended chain polymer compositionsare in the relaxed state. This is in contrast to conventional polymersolutions which may be caused to depolarize plane-polarized light whensubjected to appreciable shear.

The extended chain polymer concentration of the compositions of theinstant invention is above the "critical concentration point." The"critical concentration point" is routinely determined usingconventional concentration and viscosity measuring techniques (seeKwolek U.S. Pat. No. 3,671,542).

Another qualitative determination of the liquid crystalline character ofthese extended chain polymer compositions may be made with the nakedeye. These extended chain polymer compositions may appear turbid or hazyand yet contain no, or practically no undissolved solid. When theextended chain polymer compositions, seen under reflected ordinarylight, is disturbed by shaking or rolling the vessel containing theextended chain polymer compositions or by only slow stirring, there isproduced a characteristic, readily observed, satin-like sheen or glowwhich is observed even after the disturbance ceases, and which decreasesin intensity thereafter. This may be described as being a pearly oropalescent quality of the extended chain polymer compositions of thisinvention. Compositions which are disturbed as described above oftengive the appearance of having striations and/or graininess in thesurface. These visual effects are observed in the liquid crystallineextended chain polymer compositions of this invention. This may commonlybe referred to as "stir opalescence." Further details on qualitative andquantitative determinations of optical anisotropy are presented inKwolek U.S. Pat. No. 3,671,542.

Fiber Preparation

The liquid crystalline compositions may be formed into fibers of highquality by spinning them into suitable baths such as by wet and "airgap" spinning techniques, using spinnerets and other apparatusconstructed of materials resistant to the strong acids used. In"air-gap" spinning the spinneret is usually located in air or in aninert gaseous medium a short distance (e.g., 1 to 24 cm) above thesurface of a coagulating bath.

However, air-gaps suitable for use in the present invention may rangefrom less than about 1 cm to about 150 cm or longer, preferably fromabout 2 cm to about 300 cm, more preferably from about 10 cm to about200 cm, and most preferably from about 10 cm to about 100 cm.

In the present invention, the initial draw ratio is approximately fromabout 1:1 to about 50:1 and higher. Preferably, the initial draw ratiois from about 20:1to about 80:1, especially preferably, from about 80:1to about 200:1, and, most preferably, from about 100:1 to about 150:1.

The term "draw ratio", as is well known, is a measure of the degree ofstretching during the orientation of the fibrous material. In thepresent invention, the initial draw ratio is a measure of the degree ofstretching of the filaments which occurs between the extrusion orificesand the exit from the coagulation bath. The initial draw ratio isdefined as exit velocity divided by jet speed.

The jet speed is the speed at which the extruded polymer exits anextrusion orifice. It is conveniently determined by dividing the totalpolymer extrusion velocity by the total surface area of the extrusionorifices.

The exit velocity is the speed at which the filaments leave thecoagulation bath. Although any means of measurement may be used, theexit velocity is conveniently determined by the surface speed of therolls which take up the filaments after their exit from the bath. Thus,the speed of the wash rolls is preferably measured for this purpose.

Spinning of polybenzimidazole fibers by one working of this generaltechnique is described in, e.g. Tan U.S. Pat. No. 4,283,245. A varietyof baths may be used to coagulate the extruded dope into fibers. Thebaths may be, e.g., water or methanol and the like, or a dilute solutionof a mineral acid (for example, phosphoric acid or sulfuric acid and thelike). Preferably, the temperature of a coagulation bath is roomtemperature or below.

It is desirable to completely remove the spinning solvent from fibersamples prepared from the liquid crystalline compositions of thisinvention. Water alone or aqueous alkaline solutions may be used forremoval of the residual acid. A convenient method is to spray thethreadline as it leaves the coagulating bath with an aqueous alkalinesolution (e.g., saturated sodium bicarbonate), remove the surface liquidfrom the threadline with a wiping device (e.g., a sponge) or a jet, washwith water and/or aqueous alkaline solutions to reduce the acid content,and wind up the fibers on bobbins. The fibers may be soaked in water fora period sufficient to remove the acid. The thoroughly washed fibers maybe dried on the bobbin in the area of temperatures of up to about 110°C. They can also be conveniently dried on heated rolls.

The liquid crystalline compositions are especially suitable forextruding. This and other methods of article fabrication are fullydescribed in J. S. Robinson, "Spinning, Extruding, and Processing ofFibers"; Chemical Technology Review No. 159, Noyes Data Corp., 1980. Theabove cited patents and/or publications are incorporated herein byreference.

The fibers prepared from the polymers of this invention exhibit highvalues of tensile properties, especially in the as-extruded state, i.e.,without subsequent hot drawing or annealing. The tensile properties ofthese as-extruded fibers can be enhanced by subjecting the undrawnfibers to a heat treatment.

Fiber Tensile Properties

Filament properties are measured on fibers that are conditioned at 21degrees C., and 65% relative humidity (R.H.) for at least 16 hoursunless otherwise specified. Yarn properties are measured on yarn thatare conditioned at 24 degrees C. and 55% R.H. for at least 16 hours. Allmeasurements are made in the fiber conditioning environment.

Tenacity (breaking tenacity) (T), elongation (breaking elongation) (E),and initial modulus (Mi) are obtained from breaking a single filament ora multifilament yarn on an Instron tester (Instron Engineering Corp.,Canton, Mass.).

Single filaments are broken with a gage length (distance between jaws)of 1.0 inch (2.54 cm.). The results on 3 filaments are averaged. Yarnsare given 3 turns per inch (2.54 cm.) twist (under 0.1 g.p.d. tension)and broken with a 10 inch (25.4 cm.) gage length. All samples areelongated at a constant rate of extension (10% elongation/minute forfibers having an E of under 8%, and 60% elongation/minute for fiberswith E of 8 to 100%) until the sample breaks.

The denier of a single filament (d.p.f.) is calculated from itsfunctional resonant frequency, determined by vibrating a 7 to 9 cm.length of fiber under tension with changing frequency (ASTM D1577-1973).This filament is then used for 1 break.

The denier of yarn is determined by weighing a known length (at 0.1g.p.d. tension); 90 cm. length is convenient.

The tenacity (grams/denier), elongation (percent) and initial modulus(gram/denier) as defined in ASTM 3379-75e are obtained from theload-elongation curve and the measured denier. In actual practice, themeasured denier of the sample, test conditions and sample identificationmaybe fed to a computer before the start of a test; the computer recordthe load-elongation curve of the fiber as it is broken and thencalculates the fiber properties.

It should be noted that different values maybe obtained from singlefilaments (filament properties) and from multifilament strands (yarnproperties) of the same sample. Unless specified otherwise allproperties given herein are filament properties.

Additives

It will be understood that the usual additives such as dyes, fillers,antioxidants, and the like can be incorporated into the compositions ofthe present invention for the purpose intended, before preparation ofthe shaped article.

Mineral acids that are solvents for the extended chain polymers of theinstant compositions such as polyphosphoric acid, methane sulfonic acid,100% sulfuric acid, chlorosulfonic acid, and the like, may be added tothe compositions of the invention in minor amounts (without departingfrom the scope of the invention) for purposes of modifying conditionsfor processing into shaped articles. The strong acid additives maycontain one or more of the acid-soluble polymers described in Helmimiak,et al., U.S. Pat. No. 4,207,407 sad P. D. Sybert, "Rigid-RodPolyquinolines: Synthesis, Structure-Property Relationships andHigh-Strength Fibers", Colorado State University, Ph.D. Thesis, 1980.The above cited patent and thesis are incorporated herein by reference.

4. Industrial Applicability

The liquid crystalline extended chain polymer compositions are extremelysuitable for spinning into highly ordered and high strength fibers. Suchfibers are useful as reinforcement substitutes for other inorganic ororganic products. Various examples include glass fibers, asbestos, boronfibers, carbon and graphite fibers, whiskers, quartz and silica fibers,ceramic fibers, metal fibers, natural orgasmic fibers, and syntheticorganic fibers. A reinforcement may be defined simply as the materialthat is added to a resinous matrix to improve the strength and otherphysical and chemical properties of the material.

Furthermore, the polymers of the instant compositions can be employed inany use typically performed by engineering thermoplastic materials, suchas metal replacements and those areas where high performance isnecessary. Extended chain polymer compositions may be employed for usein forming high strength films suitable in the production of composites,belts, tires, i.e., as tire cords, and the like. The films are suitableas construction materials for rocket nose cones and various other partsof space craft.

Depending on the extended chain polymer fiber or films selected (i.e.,homopolymer, copolymer, block polymer, or mixture thereof) theproperties of the article formed may be controlled to suit the desireduse. The control of polymer properties is an advantage, since, in thevarious areas of utility for such polymers, e.g., as laminates,structural materials, adhesives and ablative materials, the needs varyconsiderably.

By way of comparison. Examples 1-5 below are illustrative of lowmolecular weight (i.e., low intrinsic viscosity) and/or low polymerconcentration compositions.

EXAMPLE 1

In a 6-L resin flask were placed 386.76 g (1.5774 mol) of2,5-diamino-1,4-benzenedithiol dihydrochloride (1a) and 2.98 kg offreshly prepared PPA. The PPA was prepared as described in Wolfe andArnold, Macromolecules, Vol 14, 909 (1981). The mixture was stirred atroom temperature under a flow of argon for 24h and heated a 60°-70° C.for 34h. The resulting solution was clear with no evidence of bubbles.Terephthalic acid (262.35 g, 1.5792 mol) was then added and incorporatedinto the solution by rapid stirring at 110° C. Additional PPA (4.1 kg)was then added. The yellow mixture was heated as follows: 110°-165° C.in 5h, 165° C. for 12h, 180° C. for 12h, and 195° C. for 12h. Themixture became stir-opalescent after 6h at polymerization temperatures.Reduced pressure was applied during the first 6 h of reaction but wasalternated with an argon stream such that the mixture did not foam abovea predetermined flask wall level. The hazy green product exhibitingyellow-green opalescence was removed from the flask and precipitatedinto a large volume of water. The copper-colored polymer was washeduntil the water was no longer acidic and then dried at 80°-100° C. underreduced pressure for 48h. A portion of the reaction product was bottledfor use in fiber-spinning studies: intrinsic viscosity [η]=30.3 dL/g(MSA). Anal.Calcd for C₁₄ H₆ N₂ S₂ ; C,63.13; H,2.27; N,10.51; S,24.08.Found: C,82.75; H, 2.346; N, 10.24; S, 23.22. The foregoing procedureprovided a 5.6 wt % of polymer --AI--_(n) in PPA. Polymerizationmixtures of higher polymer concentration (up to 10%) were prepared.These runs required higher monomer 1a concentration duringdehydrochlorination. Intermittent cooling was cycled with argon pressureas required to control foaming at the desired level in the reactionvessel. Similarly, polymer --AI--_(n) in PPA of lower concentration wereprepared and these required less time for complete dehydrochlorinationthan that described.

EXAMPLE 2

In a 6-L resin flask were placed 919.94 g (3.7519 mol) of 1a andapproximately 2.7 kg of 115% PPA; the % P₂ O₅ content profile for thisExample is illustrated in FIG. 8.

The 115% PPA was obtained from FMC Corporation and heated to 150° C.under an argon atmosphere, heated at 150° C. under reduced pressure for18h, and cooled to room temperature immediately before use. The viscousmixture was stirred and an ice bath was applied for 24h to preventvigorous foaming. Five additional days of stirring at room temperaturewere required to remove enough hydrogen chloride to allow heating aboveroom temperature. A clear, viscous solution was obtained after heatingfor 18h at 80° C. Finely powdered 2a (622.90 g, 3.7454 mol) and anadditional 2.773 g of the above 115% PPA were then added. The mixturewas then stirred and heated to 140° C. for 3h and then heated at150°-160° C. for 16h. The mixture gradually darkened, became opticallyisotropic, and never became noticeably more viscous. Samples that wereremoved and precipitated in water gave a dark green non-fibrousmaterial. Additional heating failed to increase the viscosity to anextent to yield a fibrous material. The theoretical polymerconcentration --AI--_(n) for this experiment was 14.8% in a PPA with anintermediate P₂ O₅ content of 83.8% and a final of 79.8%.

EXAMPLE 3

To a 100 mL flask containing 15.8 g of concentrated orthophosphoric acid(85.4% H₃ PO₄) that had been cooled in an ice bath was added 24.2 g ofphosphorus pentoxide and the mixture heated at 150° C. for 6h under anargon atmosphere. The % P₂ O₅ content profile for this Example isillustrated in FIG. 9.

After cooling the PPA (84.9% P₂ O₅) to room temperature, 6.0 g (0.029mol) of 4-amino-3-mercaptobenzoic acid hydrochloride (3a) (prepared bythe method of Wolfe, AFOSR Final Technical Report, Dec. 15, 1980) wasadded and the viscous mixture stirred at 40° C. for 24h. The mixture wasthen placed under reduced pressure and the temperature slowly raised to70° C. The orange-yellow mixture was then heated to 150° C. over a 2hperiod. The resulting dark red solution was optically isotropic. Thesolution was then stirred at 150° C. for an additional 24h. The polymerwas isolated from the resulting optically isotropic solution containing8.6% of the polymer by precipitation with water to give brittle films.The intrinsic viscosity of the isolated polymer --T--_(n) was 3.0 dL/gin methanesulfonic acid at 30° C.

EXAMPLE 4

To a 50 mL round bottom flask containing 48.15 g of PPA that wasprepared as described in Wolfe and Arnold, Macromolecules, Vol. 14, 909(1981) was added 7.436 g (0.03616 mol) of 4-amino-3-mercaptobenzoic acidhydrochloride (3a) that was prepared as described in Wolfe, AFOSR FinalTechnical Report, Dec. 15, 1980. The mixture was stirred at roomtemperature under an argon flow for 18h. After stirring for 2h underreduced pressure between 50° and 80° C. the solution was a clear orangecolor. The solution was then heated under reduced pressure as follows:90° C. for 0.5h; 100° C. for 0.5h; 110° C. for 0.5h; 130° C. for 0.5h;140° C. for 0.5h; 180° C. for 8h; 150° C. for 5h; 190° C. for 16h; 180°C. for 16h; 160° C. for 16h; 200° C. for 200h and 170° C. for 7h. Theresulting isotropic solution having a concentration of polymer --T--_(n)of 9.4% by weight gave only brittle amorphous films when precipitated inwater. The intrinsic viscosity of the isolated polymer was 3.80 dL/g inmethanesulfonic acid at 30.0° C.

EXAMPLE 5

To 38 g of PPA that was prepared as described in Wolfe and Arnold,Macromolecules, Vol. 14, 909 (1981) was added 1.421 g (8.41 mmol) of4-amino-3-mercaptobenzoic acid (3b) that was prepared by neutralizationof an aqueous suspension of 4-amino-3-mercaptobenzoic acid hydrochloride(3a) (prepared according to Wolfe, AFOSR Final Technical Report, Dec.15, 1980) followed by extraction with ethyl acetate, evaporation of theethyl acetate, and recrystallization of the pale yellow residue frommethylene chloride. The viscous mixture was heated to 140° C. under anargon flow in a 0.5h period. The temperature was raised to 160° C. overa 0.5h period and then maintained at 160° C. for 18h under reducedpressure. The optically isotropic, red solution was then heated underreduced pressure for 8h at 200° C. The isolated polymer --T--_(n) had anintrinsic viscosity of 4.57 dL/g in MSA at 30.0° C.

The compositions of this invention, their production and theiradvantages and uses are further illustrated in the following examples.These are intended only to demonstrate the invention and are not to beconstrued as limiting its scope, which scope is instead defined by theappended claims.

All polyphosphoric acid (PPA) hereinafter referred to as 115% wasobtained from FMC Corporation and used as received. Terephthalic acid(2a) was obtained from Amoco Chemicals Company, reduced to an averageparticle size of 95% <10 um by an air-impact method, and dried beforeuse. All monomers and P₂ O₅ that were added to PPA were deaerated byplacing them in a desiccator, applying reduced pressure, filling with aninert gas, and repeating the procedure at least once.

EXAMPLE 6

A mixture of 88.2 g of concentrated orthophosphoric acid (85.4% H₃ PO₄)and 205.2 g of 115% PPA was stirred at 100° C. for 2h under reducedpressure. After allowing the PPA solution to cool to approximately 50°C. a portion of this solution (282.1 g) was added to a 500 mL resinkettle containing 53.01013 g (0.21620 mol) of 1a. After stirring toincorporate the solid monomer into the PPA, the mixture was stirred atroom temperature for 2h under argon and then under reduced pressure at:25°-30° C. for 24h; 50° C. for 3h; and 70° C. for 16h. Monomer 2a(35.91734 g, 0.216196 mol) was then added to the resulting clear lightgreen solution in four portions. After the addition of each portion, thereaction kettle was placed under reduced pressure before the 2a wasincorporated by stirring. The mixture was allowed to cool toapproximately 50° C. before 118.3 g of P₂ O₅ was added to increase theeffective P₂ O₅ content to 83.9%. The viscous slurry was then heated asfollows: 100°-170° C. in 3h; 170° C. for 17h; 185° C. for 5h; and 200°C. for 19h. The intrinsic viscosities (in dL/g) of the polymer--AI--_(n) were determined from samples of the polymer solutionwithdrawn at the polymerization times indicated: 9.2 (8.5h), 12.6(25.5h), 15.8 (44.0h). Heating this reaction solution at 200° C. for anadditional 76h only increased the intrinsic viscosity of the --AI--_(n)component to 16.4 dL/g. The reaction product is characterized as havinga final P₂ O₅ content of approximately 80.8% with the --AI--_(n) anpolymer concentration being approximately 12.6 wt %.

EXAMPLE 7

A mixture of 57.3 g of concentrated orthophosphoric acid (85.4% H₃ PO₄)and 133.7 g of 115% PPA was stirred at 100° C. for 4h under reducedpressure. After allowing the PPA solution to cool to room temperature, aportion of this solution (185.0 g) was added to a 500 mL resin kettlecontaining 53.61422 g (0.21866 mol) of 1a. (Monomer 1a of small crystalsize was prepared without a final recrystallization according to themethod of Wolfe, Loo, and Arnold, Macromolecules Vol. 14, 915 (1981)using the final isolation procedure involving the transfer of thedipotassium salt of 1a as an aqueous solution into 6N hydrochloricacid.)

After stirring to incorporate the monomer into the PPA, the mixture wasstirred at 55°-65° C. for 5.5h under reduced pressure, at 25° C. for15.5h under an argon flow, and at 65°-72° C. for 4h under reducedpressure. Monomer 2a (36.3268 g, 0.21866 mol) was added to the resinkettle containing the dehydrochlorinated solution of monomer 1a in PPA.After the addition of each of the six portions, the incorporation of thesolid into the solution was aided by placing the kettle under reducedpressure before stirring was initiated. Powdered phosphorus pentoxide(114.4 g) was then added to increase the effective P₂ O₅ content to86.4% and the mixture was stirred at 100° C. for 27h. The polymerizationmixture was then heated as follows: 100°-170° C. in 1h; 170° C. for21.5h; and 200° C. for 71.5h. The intrinsic viscosities (in dL/g) of thepolymer --AI--_(n) were determined from samples withdrawn at thepolymerization times indicated: 23.1 (22.5h), 24.8 (29.0h), 27.0 (94h).The reaction product is characterized as having a final effective P₂ O₅content of approximately 82.2% and a polymer --AI--_(n) concentrationbeing approximately 15.2 wt %.

EXAMPLE 8

182.7 g of a PPA solution with an effective P₂ O₅ content of 77.2%(prepared by mixing 30 wt % of H₃ PO₄ and 70 wt % of 115% PPA) was addedto a 500 mL resin kettle containing 52.62853 g (0.21460 mol) of 1a.(Monomer 1a of large crystal size was prepared with a finalrecrystallization according to the method of Wolfe, Loo, and Arnold,Macromolecules, 14, 915 (1981) using the final isolation procedureinvolving a transfer of the dipotassium salt of monomer 1a as solid into6N hydrochloric acid.) After stirring to incorporate the solid monomerinto the PPA, the mixture was substantially dehydrochlorinated byheating the mixture at 55°-70° C. under reduced pressure forapproximately 31h. Monomer 2a (35.6522 g, 0.21460 mol) was added to theresin kettle and incorporated as described in the previous Example.Powdered P₂ O₅ (123.35 g) was then added to increase the effective P₂ O₅content to approximately 86.4% and resulting mixture was stirred at 100°C. for 17h under an argon flow. The polymerization mixture was thenheated with stirring as follows: 100°-170° C. in 1h, 170° C. for 23h,and 200° C. for 24h. The intrinsic viscosities (in dL/g) were determinedfor the --AI--_(n) polymer from samples withdrawn at the indicatedtimes: 17.2 (7h), 22.8 (24h), and 35.4 (48h). Heating without stirringfor an additional 24h did not increase the intrinsic viscosity of the--AI--_(n) polymer. The green reaction product exhibits stir-opalescenceand is characterized as having a final effective P₂ O₅ content of 82.2%with --AI--_(n) polymer concentration being approximately 15.1 wt %.

EXAMPLE 9

A mixture of 4.925 g of concentrated orthophosphoric acid (85.4% H₃ PO₄)and 11,491 g of 115% PPA was stirred in a 22L flask for 5h at 100° C.under reduced pressure. After allowing the PPA solution to cool to 50°C. under a flow of argon, a portion of this solution (11.321 g) wasadded to a 40-L glass resin kettle (equipped with a mechanical stirrerconsisting of a 3/4 hp variable speed drive and stirring blades made ofHastelloy C-276) containing 2,380.55 g (9.7088 mol) of 1a prepared asdescribed in Example 7. The mixture was then stirred at: 65° C. for 17hunder a flow of argon; 65° C. for 2h at 700-400 mm Hg; and 65° C. for 2hat 40 mm Hg. An additional 2,552.77 g (10.4112 mol) of monomer 1a thathad been prepared and deaerated as described in Example 8 was then addedunder a flow of argon.

An additional 4,874 g of the above-mentioned PPA was added and themixture stirred at: 65° C. for 1h at 700-300 mm Hg; 65°-70° C. for 3.25hat 40 mm Hg; 70° C. for 2.5h at less than 5 mm Hg; 700° C. for 7.5hunder a flow of argon; and 80° C. for 26h at less than 5 mm Hg. Monomer2a (3,342.62 g, 20.1205 mol) was then added. The resulting slurry wasthen cooled to 40° C., and 6,512.1 g of powdered P₂ O₅ was added over a4.5 period. The resulting viscous mixture was stirred at 80° C. for 17hunder an argon flow. The mixture was then heated to 100° C. and anadditional 4,655.4 g of P₂ O₅ was added to increase the effective P₂ O₅content to 86.5%. After stirring for an additional 48h at 100°-108° C.,the polymerization mixture was heated as follows: 100°-170° C. in 3h;170° C. for 20h; and 200° C. for 1.5h. The intrinsic viscosities (indL/g) were determined from samples withdrawn at the indicated reactiontimes: 17.9 (14h), 18.5 (16.5h), 19.0 (23h), 24.34 (24.5h). Additionalheating at 200° C. only increased the intrinsic viscosity to 24.6 dL/g.The reaction product exhibited stir-opalescence and is characterized ashaving a final effective P₂ O₅ content of 82.2% with the --AI--_(n)polymer concentration being approximately 15.6% by weight.

EXAMPLE 10

To a 500 mL resin kettle containing a deaerated mixture of 12.06155 g(0.0594092 mol) of terephthaloyl chloride (2b) and 14.5665 g (0.0594081mol) of 1a was added approximately 140 g of 115% PPA that had beenstirred at 100° C. under reduced pressure for 1-2h, and had cooled toroom temperature. The mixture was then stirred under an argon flow at:40° C. for 23h; 50° C. for 3h; 60° C. for 2h; 70° C. for 19h; and 80° C.for 3h. The solution was then stirred at 80° C. under reduced pressurefor 1h. An additional 140 g of deaerated 115% PPA was then incorporatedinto the solution. The polymerization was stirred under argon at: 100°C. for 30 min; 110° C. for 30 min; 120° C. for 30 min; 130° C. for 30min; 140° C. for 30 min; 150° C. for 30 min; 160° C. for 45 min; 170° C.for 11h; 185° C. for 5h; and 200° C. for 46.5h. Precipitation in waterof a small amount of the anisotropic product provided polymer --AI--_(n)which possessed an intrinsic viscosity of 17.7 (dL/g) in MSA at 30° C.

EXAMPLE 11

A mixture of 74.52 g of 85.7% orthophosphoric acid and 173.88 g of 115%PPA (83.8% P₂ O₅ content) is stirred under reduced pressure for 2h at100° C. After cooling to room temperature, 55.23561 g (0.225273 mol) of1a (prepared as described in Example 8) and 45.73607 g (0.225273 mol) of2b (freshly sublimed) are added in eight portions. After the addition ofeach portion of monomer stirring is initiated to incorporate themonomer. The mixture is then stirred while the temperature is slowlyincreased and the pressure is slowly decreased until dehydrochlorinationis complete. Deaerated phosphorus pentoxide (87.54 g) is then added tothe dehydrochlorination mixture at 50° C. The mixture is then stirred at100° C. for several hours. The polymerization is then stirred under anargon atmosphere at 170° C. for approximately 20h, at 180° C. forapproximately 8h, and at 200° C. for 3h. The resulting product contains15 wt % of --AI--_(n) in PPA (82.2% P₂ O₅).

EXAMPLE 12

86.17 g of a PPA solution with an effective P₂ O₅ content of 74.9%(prepared by mixing 40 wt % of 85% H₃ PO₄ and 60 wt % of 115% PPA) wasadded to a 500 mL resin kettle containing 27.62485 g (0.112665 mol) of1a. The monomer was incorporated into the PPA solution by stirring andthe resulting mixture was then substantially dehydrochlorinated byheating the mixture at 55°-80° under reduced pressure for approximately21 hours. The % P₂ O₅ content profile for this Example is illustrated inFIG. 10. Monomer 2a (18.7208 g, 0.112686 mol) was then added to theresin kettle. Powdered P₂ O₅ (83.17 g) was then added to increase theeffective P₂ O₅ content to approximately 87.2%. The resulting yellowslurry was stirred at 100° C. for 15h under an argon flow. This slurry,which had not noticeably increased in bulk viscosity, was then stirredvigorously and heated by increasing the oil bath temperature from 100°C. to 178° C. within 40 minutes, and to 185° C. within 1h.Polymerization times indicated below begin with time above 100° C. The185° C. temperature was then maintained for 76.5h. Intrinsic viscositiesin MSA at 30° C. (in dL/g) were determined for the --AI--_(n) polymerfrom samples withdrawn at the indicated polymerization times: 16.6(1.5h), 21.7 (2.25h), 24.2 (3.25h), 35.7 (7.7h), and 42.1 (76.5h). Theintrinsic viscosity of 42.1 corresponds to an average n value ofpolymerization of about 140. The polymerization product wasstir-opalescent after a polymerization time of 0.75h and was found to behighly drawable after 1.25h. Fibers prepared by directly drawing thisproduct and precipitating the strands into water were amber,translucent, birefringent (crossed polars), showed extinction oftransmitted light when a single polaroid sheet was placed perpendicularto the fiber direction, and could be fibrillated into microfibrils.Fibers prepared after 1.5h by the same method were noticeably strongerthan the sample at 1.25h. The bulk viscosity of the product and therelaxation time of opalescence had noticeably increased after 2.25h. TheP₂ O₅ content of the PPA component of the product was approximately83.2% and the concentration of the --AI--_(n) polymer was 14.5% byweight based on the total weight of the resulting reaction product.

EXAMPLE 13

A mixture of 17.7 g of concentrated orthophosphoric acid (85.7% H₃ PO₄)and 26.6 g of 115% PPA was stirred under reduced pressure at 100° C. for2 hours. The % P₂ O₅ content profile for this Example is illustrated inFIG. 11. The resulting solution was then poured at approximately 100° C.under a stream of argon into a 200 mL resin kettle containing 11.41145 g(0.054028 mol) of 4,6-diamino-1,3-benzenediol dihydrochloride (1b) thatwas prepared according to the method of Wolfe and Arnold,Macromolecules, Vol. 14, 909 (1981), recrystallized from aqueoushydrochloric acid containing 3 wt % stannous chloride, and dried for 20hat 63° C. under reduced pressure immediately before use. The mixture wasstirred at 53° C. for 15h and 62° C. for 4h under reduced pressure. Uponheating to 70° C., the monomer precipitated. Addition of 16.6 g of P₂ O₅resulted in redissolution of the monomer. The solution was then heatedat 100° C. for 3h under reduced pressure to complete thedehydrochlorination. Monomer 2a (8.9761 g, 0.05403 mol) was then addedunder an argon flow. Additional P₂ O₅ (19.0 g) was then added. Thesolution was then heated as follows: 100° C. for 48h; 150° C. for 2.5h;160° C. for 10h (the dark green solution became stir-opalescent duringthis period); and 180° C. for 25h. The resulting reaction product wasdeep purple with a metallic luster, exhibited stir-opalescence,depolarized plane-polarized light as evidenced by strong birefringencewhen viewed between crossed polars, and is further characterized ashaving a final effective P₂ O₅ content of 82% with the --BI--_(n)polymer concentration being 13.3% by weight. The intrinsic viscosity ofthe polymer --BI--_(n) isolated from the reaction product was 23.9 dL/gin MSA at 30° C., which corresponds to an average number of recurringunits, n, of approximately 110.

EXAMPLE 14

The reaction product from Example 13 was drawn many times its length togive highly fibrillar fibers. A portion of the solution was removed fromthe reaction flask and placed in a KBr press equipped with a die with acircular orifice of 0.13 mm in diameter. The solution was extruded intothe air and stretched by pulling manually and then the fiber was dippedin water. The fiber thus produced was washed with water and then driedunder tension in an air oven overnight at 110° C. The fiber produced wasmeasured to be between 0.0093 mm and 0.012 mm in diameter. Highorientation was evident from fibrils which split from the surface of thefiber and by the complete extinction of light transmitted through thefiber when a single polaroid was placed in a perpendicular directiononly between the source and the fiber.

EXAMPLE 15

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 48.9831 g (0.19978 mol) of monomer 1a is dehydrochlorinatedin an "initial" solution of 269.68 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 80.9 g of 85.4% H₃ PO₄ with 188.8 g of 115% PPA).When dehydrochlorination is substantially complete, 79.9805 g (0.19978mol) of monomer 2s is added followed by the gradual addition of 142.23 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 85.07%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 19%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure: ##STR160##characterized by an intrinsic viscosity of 20 dL/g in MSA at 30° C.which corresponds to an n value of average polymerization of about 50.

EXAMPLE 16

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 64.4470 g (0.26284 mol) of monomer 1a is dehydrochlorinatedin an "initial" solution of 341.97 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 102.6 g of 85.4% H₃ PO₄ with 239.4 g of 115% PPA).When dehydrochlorination is substantially complete, 63.6826 g (0.26284mol) of monomer 2j is added followed by the gradual addition of 137.3 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 83.7%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 17%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure: ##STR161##characterized by an intrinsic viscosity of 15 dL/g in MSA at 30° C.which corresponds to an n value of average polymerization of about 100.

EXAMPLE 17

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 61.1619 g (0.28706 mol) of monomer 1b is dehydrochlorinatedin sa "initial" solution of 338.4 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 101.5 g of 85.4% H₃ PO₄ with 236.8 g of 115% PPA).When dehydrochlorination is substantially complete, 69.5488 g (0.28706mol) of monomer 2j is added followed by the gradual addition of 140.1 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 83.8%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 17%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure: ##STR162##characterized by an intrinsic viscosity of 16 dL/g in MSA at 30° C.which corresponds to an n value of average polymerization of about 60.

EXAMPLE 18

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 81.9923 g (0.28869 mol) of monomer 1c is dehydrochlorinatedin an "initial" solution of 366.8 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 110 g of 85.4% H₃ PO₄ with 256.8 g of 115% PPA).When dehydrochlorination is substantially complete, 69.9438 g (0.28869mol) of monomer 2j is added followed by the gradual addition of 148.4 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 83.8%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 16%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure: ##STR163##characterized by an intrinsic viscosity of 16 dL/g in MSA at 30° C.which corresponds to an n value of average polymerization of about 60.

EXAMPLE 19

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 93.8232 g (0.29202 mol) of monomer 1i is dehydrochlorinatedin an "initial" solution of 263.5 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 79.1 g of 85.4% H₃ PO₄ with 184.4 g of 115% PPA).When dehydrochlorination is substantially complete, 48.5129 g (0.29202mol) of monomer 2a is added followed by the gradual addition of 171 g ofP₂ O₅. The mixture is then stirred and heated essentially according toExample 8. The amount of P₂ O₅ is preselected (as determined in accordwith the aforementioned formulae a* and b*) to provide the reactionmixture with an effective P₂ O₅ content of approximately 86.2% prior tothe start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantially complete polymerization.The reaction produce obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 18%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure: ##STR164##characterized by an intrinsic viscosity of 15 dL/g in MSA at 30° C.

EXAMPLE 20

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 93.1836 g (0.32225 mol) of monomer 1j is dehydrochlorinatedin an "initial" solution of 254.0 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 76.2 g of 85.4% H₃ PO₄ with 177.8 g of 115% PPA).When dehydrochlorination is substantially complete, 53.5357 g (0.32225mol) of monomer 2a is added, followed by the gradual addition of 178.4 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 86.6%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantially complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 18%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure: ##STR165##characterized by an intrinsic viscosity of 14 dL/g in MSA at 30° C.

EXAMPLE 21

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 93.1836 g (0.32225 mol) of monomer 1k is dehydrochlorinatedin an "initial" solution of 254.0 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 76.2 g of 85.4% H₃ PO₄ with 177.8 g of 115% PPA).When dehydrochlorination is substantially complete, 53.5357 g (0.32225mol) of monomer 2a is added, followed by the gradual addition of 178.4 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 86.6%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantially complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 18%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure: ##STR166##characterized by an intrinsic viscosity of 14 dL/g in MSA at 30° C.

EXAMPLE 22

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 128.474 g (0.32431 mol) of monomer 11 is dehydrochlorinatedin an "initial" solution of 223.5 g PPA having a P₂ O₅ content of 79.4%(prepared by mixing 44.7 g of 85.4% H₃ PO₄ with 178.8 g of 115% PPA).When dehydrochlorination is substantially complete, 53.8778 g (0.32431mol) of monomer 2a is added, followed by the gradual addition of 197.0 gof P₂ O₅. Inorganic salts, such as lithium sales (e.g., LiCl, LiF,Lithium phosphate, and the like) can be added at this point, ifrequired, to promote polymer solubility. The mixture is then stirred andheated essentially according to Example 8. The amount of P₂ O₅ ispreselected (as determined in accord with the aforementioned formulae a*and b*) to provide the reaction mixture with an effective P₂ O₅ contentof approximately 89.1% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent tosubstantially complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 18%; fibers are readily formed by directspinning, or drawing from the reaction produce. The polymer obtained isof the following structure: ##STR167## characterized by an intrinsicviscosity of 12 dL/g in MSA at 30° C.

EXAMPLE 23

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 70.3707 g (0.21902 mol) of monomer 1i is dehydrochlorinatedin an "initial" solution of 323.1 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 96.9 g of 85.4% H₃ PO₄ with 226.2 g of 115% PPA).Sen dehydrochlorination is substantially complete, 53.0654 g (0.21902mol) of monomer 2j is added followed by the gradual addition of 125.0 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 83.6%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantially complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 18%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure: ##STR168##characterized by an intrinsic viscosity of 17 dL/g in MSA at 30° C.

EXAMPLE 24

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 68.1280 g (0.23560 mol) of monomer 1j is dehydrochlorinatedin an "initial" solution of 320.7 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 96.2 g of 85.4% H₃ PO₄ with 224.5 g of 115% PPA).When dehydrochlorination is substantially complete, 57.824 g (0.23560mol) of monomer 2j is added followed by the gradual addition of 126.9 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 83.7%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantially complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 18%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure: ##STR169##characterized by an intrinsic viscosity of 15 dL/g in MSA at 30° C.

EXAMPLE 25

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 68.1280 g (0.23560 mol) of monomer 1k is dehydrochlorinatedin an "initial" solution of 320.64 g PPA having a P₂ O₅ content of 77.2%(prepared by mixing 96.19 g of 85.4% H₃ PO₄ with 184.4 g of 115% PPA).When dehydrochlorination is substantially complete, 57.0824 g (0.23560mol) of monomer 2j is added followed by the gradual addition of 126.88 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 83.7%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.2% subsequent to substantially complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 18%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure: ##STR170##characterized by an intrinsic viscosity of 14 dL/g in MSA at 30° C.

Analogous to the foregoing Examples 6-25, other Type I extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Tables 16a, 16b,17a, 17b, and 17c. The m→, e→, and p→ denote most preferred, especiallypreferred, and preferred selected monomer reactions respectively.

                  TABLE 16a                                                       ______________________________________                                        Polymers of Type I, Class 1                                                   Polymerization Reactions:                                                      ##STR171##                                                                    ##STR172##                                                                    Monomer (1,1)                                                                           +     Monomer (2,1)                                                                             ##STR173##                                                                           Polymer I(1)                              ______________________________________                                         1a        +     2e                                                                                        ##STR174##                                                                           [AJ] .sub.n                                1a        +     2f                                                                                        ##STR175##                                                                           [AJ] .sub.n                                1a        +     2i                                                                                        ##STR176##                                                                           [AK] .sub.n                                1a        +     2k                                                                                        ##STR177##                                                                           [AB] .sub.n                                1a        +     2l                                                                                        ##STR178##                                                                           [AC] .sub.n                                1a        +     2m                                                                                        ##STR179##                                                                           [AD] .sub.n                                1a        +     2n                                                                                        ##STR180##                                                                            [AE] .sub.n                               1a        +     2o                                                                                        ##STR181##                                                                           [AF] .sub.n                                1a        +     2p                                                                                        ##STR182##                                                                           [AG] .sub.n                                1a        +     2q                                                                                        ##STR183##                                                                           [AH] .sub.n                                1a        +     2t                                                                                        ##STR184##                                                                           [AICI] .sub.n                              1a        +     2u                                                                                        ##STR185##                                                                           [AIDI] .sub.n                              1a        +     2v                                                                                        ##STR186##                                                                           [AIEI] .sub. n                             1a        +     2w                                                                                        ##STR187##                                                                           [AIFI] .sub.n                              1a        +     2x                                                                                        ##STR188##                                                                           [AIGI] .sub.n                              1a        +     2y                                                                                        ##STR189##                                                                           [AIHI] .sub.n                              1b        +     2e                                                                                        ##STR190##                                                                           [BJ] .sub.n                                1b        +     2i                                                                                        ##STR191##                                                                           [BK] .sub.n                                1b        +     2k                                                                                        ##STR192##                                                                           [B] .sub.n                                 1b        +     2l                                                                                        ##STR193##                                                                           [BC] .sub.n                                1b        +     2m                                                                                        ##STR194##                                                                           [BD] .sub.n                                1b        +     2n                                                                                        ##STR195##                                                                           [BE] .sub.n                                1b        +     2o                                                                                        ##STR196##                                                                           [BF] .sub.n                                1b        +     2p                                                                                        ##STR197##                                                                           [BG] .sub.n                                1b        +     2q                                                                                        ##STR198##                                                                           [BH] .sub.n                                1b        +     2t                                                                                        ##STR199##                                                                           [BICI] .sub.n                              1b        +     2u                                                                                        ##STR200##                                                                           [BIDI] .sub.n                              1b        +     2v                                                                                        ##STR201##                                                                           [BIEI] .sub.n                              1b        +     2w                                                                                        ##STR202##                                                                           [BIFI] .sub.n                              1b        +     2x                                                                                        ##STR203##                                                                           [BIGI] .sub.n                              1b        +     2y                                                                                        ##STR204##                                                                           [BIHI] .sub.n                              1c        +     2a                                                                                        ##STR205##                                                                            [CI] .sub.n                               1c        +     2e                                                                                        ##STR206##                                                                           [CJ] .sub.n                                1c        +     2i                                                                                        ##STR207##                                                                           [CK] .sub.n                                1c        +     2k                                                                                        ##STR208##                                                                           [BC] .sub.n                                1c        +     2l                                                                                        ##STR209##                                                                           [C] .sub.n                                 1c        +     2m                                                                                        ##STR210##                                                                           [CD] .sub.n                                1c        +     2n                                                                                        ##STR211##                                                                           [CE] .sub. n                               1c        +     2o                                                                                        ##STR212##                                                                           [CF] .sub.n                                1c        +     2p                                                                                        ##STR213##                                                                           [CG] .sub.n                                1c        +     2q                                                                                        ##STR214##                                                                           [CH] .sub.n                                1c        +     2u                                                                                        ##STR215##                                                                           [CIDI] .sub.n                              1c        +     2v                                                                                        ##STR216##                                                                           [CIEI] .sub.n                              1c        +     2w                                                                                        ##STR217##                                                                           [CIFI] .sub.n                              1c         +    2x                                                                                        ##STR218##                                                                           [CIGI] .sub.n                              1c        +     2y                                                                                        ##STR219##                                                                           [CIHI] .sub.n                              1d        +     2a                                                                                        ##STR220##                                                                           [DI] .sub.n                                1d        +     2e                                                                                        ##STR221##                                                                           [DJ] .sub.n                                1d        +     2i                                                                                        ##STR222##                                                                           [DK] .sub.n                                1d        +     2m                                                                                        ##STR223##                                                                           [D] .sub.n                                 1d        +      2n                                                                                       ##STR224##                                                                           [DE] .sub.n                                1d        +     2o                                                                                        ##STR225##                                                                           [DF] .sub.n                                1d        +     2p                                                                                        ##STR226##                                                                           [DG] .sub.n                                1d        +     2q                                                                                        ##STR227##                                                                           [DH] .sub.n                                1d        +     2v                                                                                        ##STR228##                                                                           [DIEI] .sub.n                              1d        +     2w                                                                                        ##STR229##                                                                           [DIFI] .sub.n                              1d        +     2x                                                                                        ##STR230##                                                                           [DIGI] .sub.n                              1d        +     2y                                                                                        ##STR231##                                                                           [DIHI] .sub.n                              1e        +     2a                                                                                        ##STR232##                                                                           [EI] .sub.n                                1e        +     2e                                                                                        ##STR233##                                                                           [EJ] .sub.n                                1e        +     2i                                                                                        ##STR234##                                                                           [EK] .sub.n                                1e        +     2n                                                                                        ##STR235##                                                                           [E] .sub.n                                 1e        +     2o                                                                                        ##STR236##                                                                           [EF] .sub.n                                1e        +     2p                                                                                        ##STR237##                                                                           [EG] .sub.n                                1e        +     2q                                                                                        ##STR238##                                                                           [EH] .sub.n                                1e        +     2w                                                                                        ##STR239##                                                                           [EIFI] .sub.n                              1e        +     2x                                                                                        ##STR240##                                                                           [EIGI] .sub.n                              1e        +     2y                                                                                        ##STR241##                                                                           [EIHI] .sub.n                              1f        +     2a                                                                                        ##STR242##                                                                           [FI] .sub.n                                1f        +     2e                                                                                        ##STR243##                                                                           [FJ] .sub.n                                1f        +     2i                                                                                        ##STR244##                                                                           [FK] .sub.n                                1f        +     2o                                                                                        ##STR245##                                                                           [F] .sub.n                                 1f        +     2p                                                                                        ##STR246##                                                                           [FG] .sub.n                                1f        +     2q                                                                                        ##STR247##                                                                           [FH] .sub.n                                1f        +     2x                                                                                        ##STR248##                                                                           [FIGI ] .sub.n                             1f        +     2y                                                                                        ##STR249##                                                                           [FIHI] .sub.n                              1g        +     2g                                                                                        ##STR250##                                                                           [GI] .sub.n                                1g        +     2e                                                                                        ##STR251##                                                                           [GJ] .sub.n                                1g        +     2i                                                                                        ##STR252##                                                                           [GK] .sub.n                                1g        +     2p                                                                                        ##STR253##                                                                           [G] .sub.n                                 1g        +     2q                                                                                        ##STR254##                                                                           [GH] .sub.n                                 1g       +     2y                                                                                        ##STR255##                                                                           [GIHI] .sub.n                              1h        +     2a                                                                                        ##STR256##                                                                           [HI] .sub.n                                1h        +     2e                                                                                        ##STR257##                                                                           [HJ] .sub.n                                1h        +     2i                                                                                        ##STR258##                                                                           [HK] .sub.n                                1h        +     2q                                                                                        ##STR259##                                                                           [H] .sub.n                                ______________________________________                                    

                  TABLE 16b                                                       ______________________________________                                        Polymers of Type I, Class 1                                                   Polymerization Reactions:                                                      ##STR260##                                                                    ##STR261##                                                                    Monomer (1,1)                                                                           +     Monomer (2,1)                                                                             ##STR262##                                                                           Polymer I(1)                              ______________________________________                                         1a        +     2c                                                                                        ##STR263##                                                                           [AI] .sub.n                                1a        +     2d                                                                                        ##STR264##                                                                           [AI] .sub.n                                1a        +     2g                                                                                        ##STR265##                                                                           [AJ] .sub.n                                1a        +     2h                                                                                        ##STR266##                                                                           [AJ] .sub.n                                1a        +     2r                                                                                        ##STR267##                                                                           [AI] .sub.n                                1a        +     2z                                                                                        ##STR268##                                                                           [A] .sub.n                                 1b        +     2b                                                                                        ##STR269##                                                                            [BI] .sub.n                               1b        +     2c                                                                                        ##STR270##                                                                           [BI] .sub.n                                1b        +     2d                                                                                        ##STR271##                                                                           [BI] .sub.n                                1b        +     2f                                                                                        ##STR272##                                                                           [BJ] .sub.n                                1b        +     2g                                                                                        ##STR273##                                                                           [BJ] .sub.n                                1b        +     2h                                                                                        ##STR274##                                                                           [BJ] .sub.n                                1b        +     2r                                                                                        ##STR275##                                                                           [AIBI] .sub. n                             1b        +     2s                                                                                        ##STR276##                                                                           [BI] .sub.n                                1b        +     2z                                                                                        ##STR277##                                                                           [B] .sub.n                                 1c        +     2b                                                                                        ##STR278##                                                                           [CI] .sub.n                                1c        +     2c                                                                                        ##STR279##                                                                           [CI] .sub.n                                1c        +     2d                                                                                        ##STR280##                                                                           [CI] .sub.n                                1c        +     2f                                                                                        ##STR281##                                                                           [CJ] .sub.n                                1c        +     2g                                                                                        ##STR282##                                                                           [CJ] .sub.n                                1c        +     2h                                                                                        ##STR283##                                                                           [CJ] .sub.n                                1c        +     2r                                                                                        ##STR284##                                                                           [AICI] .sub.n                              1c        +     2s                                                                                        ##STR285##                                                                           [BICI] .sub.n                              1c        +     2t                                                                                        ##STR286##                                                                           [CI] .sub.n                                1d        +     2b                                                                                        ##STR287##                                                                           [DI] .sub.n                                1d        +     2c                                                                                        ##STR288##                                                                           [DI] .sub.n                                1d        +     2d                                                                                        ##STR289##                                                                           [DI] .sub.n                                1d        +     2f                                                                                        ##STR290##                                                                           [DJ] .sub.n                                1d        +     2g                                                                                        ##STR291##                                                                           [DJ] .sub.n                                1d        +     2h                                                                                        ##STR292##                                                                           [DJ] .sub.n                                1d        +     2j                                                                                        ##STR293##                                                                           [AD] .sub.n                                1d        +     2k                                                                                        ##STR294##                                                                            [BD] .sub.n                               1d        +     2l                                                                                        ##STR295##                                                                           [CD] .sub.n                                1d        +     2r                                                                                        ##STR296##                                                                           [AIDI] .sub.n                              1d        +     2s                                                                                        ##STR297##                                                                           [BIDI] .sub.n                              1d        +     2t                                                                                        ##STR298##                                                                           [CIDI] .sub.n                              1d        +     2u                                                                                        ##STR299##                                                                           [DI] .sub.n                                1e        +     2b                                                                                        ##STR300##                                                                           [EI] .sub. n                               1e        +     2c                                                                                        ##STR301##                                                                           [EI] .sub.n                                1e        +     2d                                                                                        ##STR302##                                                                           [EI] .sub.n                                1e        +     2f                                                                                        ##STR303##                                                                           [EJ] .sub.n                                1e        +     2g                                                                                        ##STR304##                                                                           [EJ] .sub.n                                1e        +     2h                                                                                        ##STR305##                                                                           [EJ] .sub.n                                1e        +     2j                                                                                        ##STR306##                                                                           [AE] .sub.n                                1e        +     2k                                                                                        ##STR307##                                                                           [BE] .sub.n                                1e        +     2l                                                                                        ##STR308##                                                                           [CE] .sub.n                                1e        +     2m                                                                                        ##STR309##                                                                           [DE] .sub.n                                1e        +     2r                                                                                        ##STR310##                                                                           [AIEI] .sub.n                              1e        +     2s                                                                                        ##STR311##                                                                           [BIEI] .sub.n                              1e        +     2t                                                                                        ##STR312##                                                                           [CIEI] .sub.n                              1e        +     2u                                                                                        ##STR313##                                                                           [DIEI] .sub.n                              1e        +     2v                                                                                        ##STR314##                                                                           [EI] .sub.n                                1f        +     2b                                                                                        ##STR315##                                                                           [FI] .sub.n                                1f        +     2c                                                                                        ##STR316##                                                                           [FI] .sub.n                                1f        +     2d                                                                                        ##STR317##                                                                           [FI] .sub.n                                1f        +     2f                                                                                        ##STR318##                                                                           [FJ] .sub.n                                1f        +     2g                                                                                        ##STR319##                                                                            [FJ] .sub.n                               1f        +     2h                                                                                        ##STR320##                                                                           [FJ] .sub.n                                1f        +     2j                                                                                        ##STR321##                                                                           [AF] .sub.n                                1f        +     2k                                                                                        ##STR322##                                                                           [BF] .sub.n                                1f        +     2l                                                                                        ##STR323##                                                                           [CF] .sub.n                                1f        +     2m                                                                                        ##STR324##                                                                           [DF] .sub.n                                1f        +     2n                                                                                        ##STR325##                                                                           [EF] .sub. n                               1f        +     2r                                                                                        ##STR326##                                                                           [AIFI] .sub.n                              1f        +     2s                                                                                        ##STR327##                                                                           [BIFI] .sub.n                              1f        +     2t                                                                                        ##STR328##                                                                           [CIFI] .sub.n                              1f        +     2u                                                                                        ##STR329##                                                                           [DIFI] .sub.n                              1f        +     2v                                                                                        ##STR330##                                                                           [EIFI] .sub.n                              1f        +     2w                                                                                        ##STR331##                                                                           [FI] .sub.n                                1g        +     2b                                                                                        ##STR332##                                                                           [GI] .sub.n                                1g        +     2c                                                                                        ##STR333##                                                                           [GI] .sub.n                                1g        +     2d                                                                                        ##STR334##                                                                           [GI] .sub.n                                1g        +     2f                                                                                        ##STR335##                                                                           [GJ] .sub.n                                1g        +     2g                                                                                        ##STR336##                                                                           [GJ] .sub.n                                1g        +     2h                                                                                        ##STR337##                                                                           [GJ] .sub.n                                1g        +     2j                                                                                        ##STR338##                                                                           [AG] .sub.n                                1g        +     2k                                                                                        ##STR339##                                                                           [BG] .sub.n                                1g        +     2l                                                                                        ##STR340##                                                                           [CG] .sub.n                                1g        +     2m                                                                                        ##STR341##                                                                           [DG] .sub.n                                1g        +     2n                                                                                        ##STR342##                                                                           [EG] .sub.n                                1g        +     2o                                                                                        ##STR343##                                                                           [FG] .sub.n                                1g        +     2r                                                                                        ##STR344##                                                                            [AIGI] .sub.n                             1g        +     2s                                                                                        ##STR345##                                                                           [BIGI] .sub.n                              1g        +     2t                                                                                        ##STR346##                                                                           [CIGI] .sub.n                              1g        +     2u                                                                                        ##STR347##                                                                           [DIGI] .sub.n                              1g        +     2v                                                                                        ##STR348##                                                                           [EIGI] .sub.n                              1g        +     2w                                                                                        ##STR349##                                                                           [FIGI] .sub.n                              1g        +     2x                                                                                        ##STR350##                                                                           [GI] .sub. n                               1h        +     2b                                                                                        ##STR351##                                                                           [HI] .sub.n                                1h        +     2c                                                                                        ##STR352##                                                                           [HI] .sub.n                                1h        +     2d                                                                                        ##STR353##                                                                           [HI] .sub.n                                1h        +     2f                                                                                        ##STR354##                                                                           [HJ] .sub.n                                1h        +     2g                                                                                        ##STR355##                                                                           [HJ] .sub.n                                1h        +     2h                                                                                        ##STR356##                                                                           [HJ] .sub.n                                1h        +     2j                                                                                        ##STR357##                                                                           [AH] .sub.n                                1h        +     2k                                                                                        ##STR358##                                                                           [BH] .sub.n                                1h        +     2l                                                                                        ##STR359##                                                                           [CH] .sub.n                                1h        +     2m                                                                                        ##STR360##                                                                           [DH] .sub.n                                1h        +     2n                                                                                        ##STR361##                                                                           [EH] .sub.n                                1h        +     2o                                                                                        ##STR362##                                                                           [FH] .sub.n                                1h        +     2p                                                                                        ##STR363##                                                                           [GH] .sub.n                                1h        +     2r                                                                                        ##STR364##                                                                           [AIHI] .sub.n                              1h        +     2s                                                                                        ##STR365##                                                                           [BIHI] .sub.n                              1h        +     2t                                                                                        ##STR366##                                                                           [CIHI] .sub.n                              1h        +     2u                                                                                        ##STR367##                                                                           [DIHI] .sub.n                              1h        +     2v                                                                                        ##STR368##                                                                           [EIHI] .sub.n                              1h        +     2w                                                                                        ##STR369##                                                                            [FIHI] .sub.n                            ______________________________________                                    

                  TABLE 17a                                                       ______________________________________                                        Polymers of Type I, Class 2                                                   Polymerization Reactions:                                                      ##STR370##                                                                    ##STR371##                                                                    Monomer (1,2)                                                                           +     Monomer (2,1)                                                                             ##STR372##                                                                           Polymer I(2)                              ______________________________________                                         1i        +     2b                                                                                        ##STR373##                                                                           [LI] .sub.n                                1i        +     2c                                                                                        ##STR374##                                                                           [LI] .sub.n                                1i        +     2d                                                                                        ##STR375##                                                                           [LI] .sub.n                                1i        +     2e                                                                                        ##STR376##                                                                           [LJ] .sub.n                                1i        +     2f                                                                                        ##STR377##                                                                           [LJ] .sub.n                                1i        +     2g                                                                                        ##STR378##                                                                           [LJ] .sub.n                                1i        +     2h                                                                                        ##STR379##                                                                            [LJ] .sub.n                               1i        +     2i                                                                                        ##STR380##                                                                           [LK] .sub.n                                1i        +     2k                                                                                        ##STR381##                                                                           [BL] .sub.n                                1i        +     2l                                                                                        ##STR382##                                                                           [CL] .sub.n                                1i        +     2m                                                                                        ##STR383##                                                                           [DL] .sub.n                                1i        +     2n                                                                                        ##STR384##                                                                           [EL] .sub.n                                1i        +     2o                                                                                        ##STR385##                                                                           [FL] .sub.n                                1i        +     2p                                                                                        ##STR386##                                                                           [GL] .sub.n                                1i        +     2q                                                                                        ##STR387##                                                                           [HL] .sub.n                                1i        +     2r                                                                                        ##STR388##                                                                           [AILI] .sub.n                              1i        +     2s                                                                                        ##STR389##                                                                           [BILI] .sub.n                              1i        +     2t                                                                                        ##STR390##                                                                           [CILI] .sub.n                              1i        +     2u                                                                                        ##STR391##                                                                           [DILI] .sub.n                              1i        +     2v                                                                                        ##STR392##                                                                           [EILI] .sub.n                              1i        +     2w                                                                                        ##STR393##                                                                           [FILI] .sub.n                              1i        +     2x                                                                                        ##STR394##                                                                           [GILI] .sub.n                              1i        +     2y                                                                                        ##STR395##                                                                           [HILI] .sub.n                              1i        +     2z                                                                                        ##STR396##                                                                           [L] .sub.n                                 1j        +     2b                                                                                        ##STR397##                                                                           [MI] .sub.n                                1j        +     2c                                                                                        ##STR398##                                                                           [MI] .sub.n                                1j        +     2d                                                                                        ##STR399##                                                                           [MI] .sub.n                                1j        +     2e                                                                                        ##STR400##                                                                           [MJ] .sub.n                                1j        +     2f                                                                                        ##STR401##                                                                           [MJ] .sub.n                                1j        +     2g                                                                                        ##STR402##                                                                           [MJ] .sub.n                                1j        +     2h                                                                                        ##STR403##                                                                           [MJ] .sub.n                                1j        +     2i                                                                                        ##STR404##                                                                            [MK] .sub.n                               1j        +     2k                                                                                        ##STR405##                                                                           [BM] .sub.n                                1j        +     2l                                                                                        ##STR406##                                                                           [CM] .sub.n                                1j        +     2m                                                                                        ##STR407##                                                                           [DM] .sub.n                                1j        +     2n                                                                                        ##STR408##                                                                           [EM] .sub.n                                1j        +     2o                                                                                        ##STR409##                                                                           [FM] .sub.n                                1j        +     2p                                                                                        ##STR410##                                                                           [GM] .sub.n                                1j        +     2q                                                                                        ##STR411##                                                                           [HM] .sub.n                                1j        +     2r                                                                                        ##STR412##                                                                           [AIMI] .sub.n                              1j        +     2s                                                                                        ##STR413##                                                                           [BIMI] .sub.n                              1j        +     2t                                                                                        ##STR414##                                                                           [CIMI] .sub.n                              1j        +     2u                                                                                        ##STR415##                                                                           [DIMI] .sub.n                              1j        +     2v                                                                                        ##STR416##                                                                           [EIMI] .sub.n                              1j        +     2w                                                                                        ##STR417##                                                                           [FIMI] .sub.n                              1j        +     2x                                                                                        ##STR418##                                                                           [GIMI] .sub.n                              1j        +     2y                                                                                        ##STR419##                                                                           [HIMI] .sub.n                              1j        +     2z                                                                                        ##STR420##                                                                           [M] .sub.n                                 1k        +     2b                                                                                        ##STR421##                                                                           [NI] .sub.n                                1k        +     2c                                                                                        ##STR422##                                                                           [NI] .sub.n                                1k        +     2d                                                                                        ##STR423##                                                                           [NI] .sub.n                                1k        +     2e                                                                                        ##STR424##                                                                           [NJ] .sub.n                                1k        +     2f                                                                                        ##STR425##                                                                           [NJ] .sub.n                                1k        +     2g                                                                                        ##STR426##                                                                           [NJ] .sub.n                                1k        +     2h                                                                                        ##STR427##                                                                           [NJ] .sub.n                                1k        +     2i                                                                                        ##STR428##                                                                           [NK] .sub.n                                1k        +     2k                                                                                        ##STR429##                                                                            [BN] .sub.n                               1k        +     2l                                                                                        ##STR430##                                                                           [CN] .sub.n                                1k        +     2m                                                                                        ##STR431##                                                                           [DN] .sub.n                                1k        +     2n                                                                                        ##STR432##                                                                           [EN] .sub.n                                1k        +     2o                                                                                        ##STR433##                                                                           [FN] .sub.n                                1k        +     2p                                                                                        ##STR434##                                                                           [GN] .sub.n                                1k        +     2q                                                                                        ##STR435##                                                                           [HN] .sub.n                                1k        +     2r                                                                                        ##STR436##                                                                           [AINI] .sub.n                              1k        +     2s                                                                                        ##STR437##                                                                           [BINI] .sub.n                              1k        +     2t                                                                                        ##STR438##                                                                           [CINI] .sub.n                              1k        +     2u                                                                                        ##STR439##                                                                           [DINI] .sub.n                              1k        +     2v                                                                                        ##STR440##                                                                           [EINI] .sub.n                              1k        +     2w                                                                                        ##STR441##                                                                           [FINI] .sub.n                              1k        +     2x                                                                                        ##STR442##                                                                           [GINI] .sub.n                              1k        +     2y                                                                                        ##STR443##                                                                           [HINI] .sub.n                              1k        +     2z                                                                                        ##STR444##                                                                           [N] .sub.n                                 1l        +     2b                                                                                        ##STR445##                                                                           [OI] .sub.n                                1l        +     2c                                                                                        ##STR446##                                                                           [OI] .sub.n                                1l        +     2d                                                                                        ##STR447##                                                                           [OI] .sub.n                                1l        +     2e                                                                                        ##STR448##                                                                           [OJ] .sub.n                                1l        +     2f                                                                                        ##STR449##                                                                           [OJ] .sub.n                                1l        +     2g                                                                                        ##STR450##                                                                           [OJ] .sub.n                                1l        +     2h                                                                                        ##STR451##                                                                           [OJ] .sub.n                                1l        +     2i                                                                                        ##STR452##                                                                           [OK] .sub.n                                1l        +     2j                                                                                        ##STR453##                                                                           [AO] .sub.n                                1l        +     2k                                                                                        ##STR454##                                                                            [BO] .sub.n                               1l        +     2l                                                                                        ##STR455##                                                                           [CO] .sub.n                                1l        +     2m                                                                                        ##STR456##                                                                           [DO] .sub.n                                1l        +     2n                                                                                        ##STR457##                                                                           [EO] .sub.n                                1l        +     2o                                                                                        ##STR458##                                                                           [FO] .sub.n                                1l        +     2p                                                                                        ##STR459##                                                                           [GO] .sub.n                                1l        +     2q                                                                                        ##STR460##                                                                           [HO] .sub.n                                1l        +     2r                                                                                        ##STR461##                                                                           [AIOI] .sub.n                              1l        +     2s                                                                                        ##STR462##                                                                           [BIOI] .sub.n                              1l        +     2t                                                                                        ##STR463##                                                                           [CIOI] .sub.n                              1l        +     2u                                                                                        ##STR464##                                                                           [DIOI] .sub.n                              1l        +     2v                                                                                        ##STR465##                                                                           [EIOI] .sub.n                              1l        +     2w                                                                                        ##STR466##                                                                           [FIOI] .sub.n                              1l        +     2x                                                                                        ##STR467##                                                                           [GIOI] .sub.n                              1l        +     2y                                                                                        ##STR468##                                                                           [HIOI] .sub.n                              1m        +     2a                                                                                        ##STR469##                                                                           [PI] .sub.n                                1m        +     2b                                                                                        ##STR470##                                                                           [PI] .sub.n                                1m        +     2c                                                                                        ##STR471##                                                                           [PI] .sub.n                                1m        +     2d                                                                                        ##STR472##                                                                           [PI] .sub.n                                1m        +     2e                                                                                        ##STR473##                                                                           [PJ] .sub.n                                1m        +     2f                                                                                        ##STR474##                                                                           [PJ] .sub.n                                1m        +     2g                                                                                        ##STR475##                                                                           [PJ] .sub.n                                1m        +     2h                                                                                        ##STR476##                                                                           [PJ] .sub.n                                1m        +     2i                                                                                        ##STR477##                                                                           [PK] .sub.n                                1m        +     2j                                                                                        ##STR478##                                                                           [AP] .sub.n                                1m        +     2k                                                                                        ##STR479##                                                                           [BP] .sub.n                                1m        +     2l                                                                                        ##STR480##                                                                           [CP] .sub.n                                1m        +     2m                                                                                        ##STR481##                                                                           [DP] .sub.n                                1m        +     2n                                                                                        ##STR482##                                                                           [EP] .sub.n                                1m        +     2o                                                                                        ##STR483##                                                                           [FP] .sub.n                                1m        +     2p                                                                                        ##STR484##                                                                           [GP] .sub.n                                1m        +     2q                                                                                        ##STR485##                                                                           [HP] .sub.n                                1m        +     2r                                                                                        ##STR486##                                                                           [AIPI] .sub.n                              1m        +     2s                                                                                        ##STR487##                                                                           [BIPI] .sub.n                              1m        +     2t                                                                                        ##STR488##                                                                           [CIPI] .sub.n                              1m        +     2u                                                                                        ##STR489##                                                                           [DIPI] .sub.n                              1m        +     2v                                                                                        ##STR490##                                                                           [EIPI] .sub.n                              1m        +     2w                                                                                        ##STR491##                                                                           [FIPI ] .sub.n                             1m        +     2x                                                                                        ##STR492##                                                                           [GIPI] .sub.n                              1m        +     2y                                                                                        ##STR493##                                                                           [HIPI] .sub.n                              1n        +     2a                                                                                        ##STR494##                                                                           [QI] .sub.n                                1n        +     2b                                                                                        ##STR495##                                                                           [QI] .sub.n                                1n        +     2c                                                                                        ##STR496##                                                                           [QI] .sub.n                                1n        +     2d                                                                                        ##STR497##                                                                           [QI] .sub.n                                1n        +     2e                                                                                        ##STR498##                                                                           [QJ] .sub.n                                1n        +     2f                                                                                        ##STR499##                                                                           [QJ] .sub.n                                1n        +     2g                                                                                        ##STR500##                                                                           [QJ] .sub.n                                1n        +     2h                                                                                        ##STR501##                                                                           [QJ] .sub.n                                1n        +     2i                                                                                        ##STR502##                                                                           [QK] .sub.n                                1n        +     2j                                                                                        ##STR503##                                                                           [AQ] .sub.n                                1n        +     2k                                                                                        ##STR504##                                                                           [BQ] .sub.n                                1n        +     2l                                                                                        ##STR505##                                                                           [CQ] .sub.n                                1n        +     2m                                                                                        ##STR506##                                                                           [DQ] .sub.n                                1n        +     2n                                                                                        ##STR507##                                                                           [EQ] .sub.n                                1n        +     2o                                                                                        ##STR508##                                                                           [FQ] .sub.n                                1n        +     2p                                                                                        ##STR509##                                                                           [GQ] .sub.n                                1n        +     2q                                                                                        ##STR510##                                                                           [HQ] .sub.n                                1n        +     2r                                                                                        ##STR511##                                                                           [AIQI] .sub.n                              1n        +     2s                                                                                        ##STR512##                                                                           [BIQI] .sub.n                              1n        +     2t                                                                                        ##STR513##                                                                           [CIQI] .sub.n                              1n        +     2u                                                                                        ##STR514##                                                                           [DIQI] .sub.n                              1n        +     2v                                                                                        ##STR515##                                                                           [EIQI] .sub.n                              1n        +     2w                                                                                        ##STR516##                                                                           [FIQI ] .sub.n                             1n        +     2x                                                                                        ##STR517##                                                                           [GIQI] .sub.n                              1n        +     2y                                                                                        ##STR518##                                                                           [HIQI] .sub.n                              1n        +     2z                                                                                        ##STR519##                                                                           [Q] .sub.n                                 1o        +     2a                                                                                        ##STR520##                                                                           [RI] .sub.n                                1o        +     2b                                                                                        ##STR521##                                                                           [RI] .sub.n                                1o        +     2c                                                                                        ##STR522##                                                                           [RI] .sub.n                                1o        +     2d                                                                                        ##STR523##                                                                           [RI] .sub.n                                1o        +     2e                                                                                        ##STR524##                                                                           [RJ] .sub.n                                1o        +     2f                                                                                        ##STR525##                                                                           [RJ] .sub.n                                1o        +     2g                                                                                        ##STR526##                                                                           [RJ] .sub.n                                1o        +     2h                                                                                        ##STR527##                                                                           [RJ] .sub.n                                1o        +     2i                                                                                        ##STR528##                                                                           [RK] .sub.n                                1o        +     2j                                                                                        ##STR529##                                                                           [AR] .sub.n                                1o        +     2k                                                                                        ##STR530##                                                                           [BR] .sub.n                                1o        +     2l                                                                                        ##STR531##                                                                           [CR] .sub.n                                1o        +     2m                                                                                        ##STR532##                                                                           [DR] .sub.n                                1o        +     2n                                                                                        ##STR533##                                                                           [ER] .sub.n                                1o        +     2o                                                                                        ##STR534##                                                                           [FR] .sub.n                                1o        +     2p                                                                                        ##STR535##                                                                           [GR] .sub.n                                1o        +     2q                                                                                        ##STR536##                                                                           [HR] .sub.n                                1o        +     2r                                                                                        ##STR537##                                                                           [AIRI] .sub.n                              1o        +     2s                                                                                        ##STR538##                                                                           [BIRI] .sub.n                              1o        +     2t                                                                                        ##STR539##                                                                           [CIRI] .sub.n                              1o        +     2u                                                                                        ##STR540##                                                                           [DIRI] .sub.n                              1o        +     2v                                                                                        ##STR541##                                                                           [EIRI ] .sub.n                             1o        +     2w                                                                                        ##STR542##                                                                           [FIRI] .sub.n                              1o        +     2x                                                                                        ##STR543##                                                                           [GIRI] .sub.n                              1o        +     2y                                                                                        ##STR544##                                                                           [HIRI] .sub.n                              1o        +     2z                                                                                        ##STR545##                                                                           [R] .sub.n                                 1p        +     2a                                                                                        ##STR546##                                                                           [SI] .sub.n                                1p        +     2b                                                                                        ##STR547##                                                                           [SI] .sub.n                                1p        +     2c                                                                                        ##STR548##                                                                           [SI] .sub.n                                1p        +     2d                                                                                        ##STR549##                                                                           [SI] .sub.n                                1p        +     2e                                                                                        ##STR550##                                                                           [SJ] .sub.n                                1p        +     2f                                                                                        ##STR551##                                                                           [SJ] .sub.n                                1p        +     2g                                                                                        ##STR552##                                                                           [SJ] .sub.n                                1p        +     2h                                                                                        ##STR553##                                                                           [SJ] .sub.n                                1p        +     2i                                                                                        ##STR554##                                                                           [SK] .sub.n                                1p        +     2j                                                                                        ##STR555##                                                                           [AS] .sub.n                                1p        +     2k                                                                                        ##STR556##                                                                           [BS] .sub.n                                1p        +     2l                                                                                        ##STR557##                                                                           [CS] .sub.n                                1p        +     2m                                                                                        ##STR558##                                                                           [DS] .sub.n                                1p        +     2n                                                                                        ##STR559##                                                                           [ES] .sub.n                                1p        +     2o                                                                                        ##STR560##                                                                           [FS] .sub.n                                1p        +     2p                                                                                        ##STR561##                                                                           [GS] .sub.n                                1p        +     2q                                                                                        ##STR562##                                                                           [HS] .sub.n                                1p        +     2r                                                                                        ##STR563##                                                                           [AISI] .sub.n                              1p        +     2s                                                                                        ##STR564##                                                                           [BISI] .sub.n                              1p        +     2t                                                                                        ##STR565##                                                                           [CISI] .sub.n                              1p        +     2u                                                                                        ##STR566##                                                                           [DISI ] .sub.n                             1p        +     2v                                                                                        ##STR567##                                                                           [EISI] .sub.n                              1p        +     2w                                                                                        ##STR568##                                                                           [FISI] .sub.n                              1p        +     2x                                                                                        ##STR569##                                                                           [GISI] .sub.n                              1p        +     2y                                                                                        ##STR570##                                                                           [HISI] .sub.n                             ______________________________________                                    

                  TABLE 17b                                                       ______________________________________                                        Polymers of Type I, Class 2                                                   Polymerization Reactions:                                                      ##STR571##                                                                    ##STR572##                                                                    Monomer (1,1)                                                                           +     Monomer (2,2)                                                                             ##STR573##                                                                           Polymer I(2)                              ______________________________________                                         1a        +     2hh                                                                                       ##STR574##                                                                           [AVIV'] .sub.n                             1a        +     2ii                                                                                       ##STR575##                                                                           [ATIT'] .sub.n                             1a        +     2jj                                                                                       ##STR576##                                                                           [ATKT'] .sub.n                             1b        +     2hh                                                                                       ##STR577##                                                                           [BVIV'] .sub.n                             1b        +     2ii                                                                                       ##STR578##                                                                           [BTIT'] .sub.n                             1b        +     2jj                                                                                       ##STR579##                                                                           [BTKT'] .sub.n                             1c        +     2hh                                                                                       ##STR580##                                                                           [CVIV'] .sub.n                             1c        +     2ii                                                                                       ##STR581##                                                                           [CTIT'] .sub.n                             1c        +     2jj                                                                                       ##STR582##                                                                           [CTKT'] .sub.n                             1d        +     2hh                                                                                       ##STR583##                                                                           [DVIV'] .sub.n                             1d        +     2ii                                                                                       ##STR584##                                                                           [DTIT'] .sub.n                             1d        +     2jj                                                                                       ##STR585##                                                                           [DTKT'] .sub.n                             1e        +     2hh                                                                                       ##STR586##                                                                           [EVIV'] .sub.n                             1e        +     2ii                                                                                       ##STR587##                                                                           [ETIT'] .sub.n                             1e        +     2jj                                                                                       ##STR588##                                                                           [ETKT'] .sub.n                             1f        +     2hh                                                                                       ##STR589##                                                                           [FVIV'] .sub.n                             1f        +     2ii                                                                                       ##STR590##                                                                           [FTIT'] .sub.n                             1f        +     2jj                                                                                       ##STR591##                                                                           [FTKT'] .sub.n                             1g        +     2hh                                                                                       ##STR592##                                                                            [GVIV'] .sub.n                            1g        +     2ii                                                                                       ##STR593##                                                                           [GTIT'] .sub.n                             1g        +     2jj                                                                                       ##STR594##                                                                           [GTKT'] .sub.n                             1h        +     2hh                                                                                       ##STR595##                                                                           [HVIV'] .sub.n                             1h        +     2ii                                                                                       ##STR596##                                                                           [HTIT'] .sub.n                             1h        +     2jj                                                                                       ##STR597##                                                                           [HTKT'] .sub.n                            ______________________________________                                    

                  TABLE 17c                                                       ______________________________________                                        Polymers of Type I, Class 2                                                   Polymerization Reactions:                                                      ##STR598##                                                                    ##STR599##                                                                    Monomer (1,2)                                                                           +     Monomer (2,2)                                                                             ##STR600##                                                                           Polymer I(2)                              ______________________________________                                         1i        +     2hh                                                                                       ##STR601##                                                                           [LVIV'] .sub.n                             1i        +     2ii                                                                                       ##STR602##                                                                           [LTIT'] .sub.n                             1i        +     2jj                                                                                       ##STR603##                                                                           [LTKT'] .sub.n                             1j        +     2hh                                                                                       ##STR604##                                                                           [MVIV'] .sub.n                             1j        +     2ii                                                                                       ##STR605##                                                                           [MTIT'] .sub.n                             1j        +     2jj                                                                                       ##STR606##                                                                           [MTKT'] .sub.n                             1k        +     2hh                                                                                       ##STR607##                                                                           [NVIV'] .sub.n                             1k        +     2ii                                                                                       ##STR608##                                                                           [NTIT'] .sub.n                             1k        +     2jj                                                                                       ##STR609##                                                                           [NTKT'] .sub.n                             1l        +     2hh                                                                                       ##STR610##                                                                           [OVIV'] .sub.n                             1l        +     2ii                                                                                       ##STR611##                                                                           [OTIT'] .sub.n                             1l        +     2jj                                                                                       ##STR612##                                                                           [OTKT'] .sub.n                             1m        +     2hh                                                                                       ##STR613##                                                                           [PVIV'] .sub.n                             1m        +     2ii                                                                                       ##STR614##                                                                           [PTIT'] .sub.n                             1m        +     2jj                                                                                       ##STR615##                                                                           [PTKT'] .sub.n                             1n        +     2hh                                                                                       ##STR616##                                                                           [QVIV'] .sub.n                             1n        +     2ii                                                                                       ##STR617##                                                                           [QTIT'] .sub.n                             1n        +     2jj                                                                                       ##STR618##                                                                           [QTKT'] .sub.n                             1o        +     2hh                                                                                       ##STR619##                                                                            [RVIV'] .sub.n                            1o        +     2ii                                                                                       ##STR620##                                                                           [RTIT'] .sub.n                             1o        +     2jj                                                                                       ##STR621##                                                                           [RTKT'] .sub.n                             1p        +     2hh                                                                                       ##STR622##                                                                           [SVIV'] .sub.n                             1p        +     2ii                                                                                       ##STR623##                                                                           [STIT'] .sub.n                             1p        +     2jj                                                                                       ##STR624##                                                                           [STKT'] .sub.n                            ______________________________________                                    

EXAMPLE 26

A solution consisting of 63.34 g concentrated phosphoric acid and 147.59g of 115% PPA was stirred at 100° C. under reduced pressure for 3h in a300 ml 3-necked flask. To a 500 mL resin kettle was added 63.49 g(0.3087 mol) of 4-amino-3-mercaptobenzoic acid hydrochloride (3a)(prepared by the method of Wolfe, AFOSR Final Technical Report, Dec. 15,1980). A portion of the above-prepared PPA having a P₂ O₅ of 77.3%(207.57 g) was poured into the resin kettle containing the monomer whileunder argon flow. After the monomer had been incorporated, a secondportion of monomer (30.71 g, 0.1493 mol) was added. The mixture washeated to 55° C. and the pressure was gradually decreased over 1.5h. Anadditional 5.35 g of monomer was added to the kettle under argon flowbringing the total monomer added to 99.65 g (0.4845 mol). The mixturewas then stirred under reduced pressure at 50° C. overnight. Thetemperature was then raised to 70° C. for 8h. Phosphorus pentoxide(138.62 g) was then added in one portion to increase the effective P₂ O₅content to 86.4%. After heating at 100° C. with stirring overnight thereaction product was stir-opalescent. After placing the mixture, whichstill contained undissolved monomer, under reduced pressure for 3h, asample was removed and was placed between a microscope slide and a coverglass. The unprecipitated product depolarized plane-polarized light. Thereaction mixture was then heated under argon as follows: an additional2.5h at 100° C.; 2h at 120 ° C.; 16h at 130° C.; 31h at 170° C.; 43.5hat 200° C. A sample of the green, opalescent polymer reaction productyielded gold-orange fibers upon precipitation in water. The sample wasextracted in water for 24h and dried under vacuum at 140° C. for 24h.The intrinsic viscosity was determined to be 8.2 dL/g in MSA at 30.1° C.The reaction product is characterized as having a final effective P₂ O₅content of 82.2% with the polymer --T--_(n) having a concentration of15.1% by weight.

EXAMPLE 27

A mixture of 125.8 g of 115% PPA and 53.9 g of concentrated phosphoricacid (85.7% H₃ PO₄) was heated to 100° C. for 4h under reduced pressurein a 500 mL 3-necked flask. The % P₂ O₅ content profile for this Exampleis illustrated in FIG. 12. To a 500 mL resin kettle was added 91.85 g(0.4466 mol) of 3a. The kettle containing the monomer was deaerated.108.17 g of the PPA prepared above (having a P₂ O₅ content of 77.2%) wasthen added. The kettle was then heated with an oil bath at 50° C. undera thin stream of argon overnight. The kettle was then placed underreduced pressure again and heated to 70° C. for 23h. P₂ O₅ (108.32 g)was then added in three portions to increase the effective P₂ O₅ contentto 88.5%. Reduced pressure was applied to degas the P₂ O₅ and to causefoaming that aided in mixing. After 3h of stirring the temperature wasraised to 100° C. and maintained at that temperature under reducedpressure for 21h. The mixture was stir-opalescent and depolarizedplane-polarized light. The mixture was then heated as follows: 115° C.under argon for 3h; 130° C. under reduced pressure for 2h; 170° C. for0.5h; 190° C. for 17h. A sample of the green, opalescent reactionproduct was removed and gave a fibrillar, golden-colored fiber upondrawing followed by precipitation in water. After extracting with waterin a Soxhlet apparatus for 24h the sample was dried for 24h at 110° C.under reduced pressure. The intrinsic viscosity of this sample was 15.8dL/g in MSA at 30.0° C. An additional 7.5h of heating gave a sample withan intrinsic viscosity of 16.7 dL/g. The reaction product thus obtainedwas 20.3% by weight of polymer --T--_(n) in PPA with a final P₂ O₅content of 82.4%.

EXAMPLE 28

The procedure of Example 27 is essentially repeated. Instead of monomer3a, 146.9123 g (0.4305753 mol) of monomer 3k is dehydrochlorinated in an"initial" solution of 265.9 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 78.6 g of 85.4% H₃ PO₄ with 187.4 g of 115% PPA).When dehydrochlorination is substantially complete, an additional 144.85g of P₂ O₅ is gradually added to the mixture and dissolved by stirringand heating essentially according to the schedule given in Example 27.The amount of P₂ O₅ added is preselected (as determined in accord withthe aforementioned formulae a* and b*) to provide the reaction mixturewith an effective P₂ O₅ content of approximately 85.3% prior to thestart of polymerization and an effective P₂ O₅ content of approximately82.2% subsequent to substantial complete polymerization. The reactionproduct obtained exhibits stir-opalescence and is further characterizedas having a polymer concentration of 19%; fibers are readily formed bydirect spinning, or drawing from the reaction product. The polymerobtained is of the following structure: ##STR625## characterized by anintrinsic viscosity of 15 dL/g in MSA at 30° C. which corresponds to anaverage n value of polymerization of about 70.

EXAMPLE 29

The procedure of Example 27 is essentially repeated. Instead of monomer3a, 161.90 g (0.85391 mol) of monomer 3c is dehydrochlorinated in an"initial" solution of 198.8 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 58.7 g of 85.4% H₃ PO₄ with 140.0 g of 115% PPA).When dehydrochlorination is substantially complete, an additional 196.8g of P₂ O₅ is gradually added to the mixture and dissolved by stirringand heating essentially according to Example 27. The amount of P₂ O₅added is preselected (as determined in accord with the aforementionedformulae a* and b*) to provide the reaction mixture with an effective P₂O₅ content of approximately 88.6% prior to the start of polymerizationand an effective P₂ O₅ content of approximately 82.2% subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 19%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure: ##STR626## characterized by an intrinsicviscosity of 12 dL/g in MSA at 30° C.

EXAMPLE 30

The procedure of Example 27 is essentially repeated. Instead of monomer3a, 161.90 g (0.85391 mol) of monomer 3d is dehydrochlorinated in an"initial" solution of 221.7 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 65.50 g of 85.4% H₃ PO₄ with 156.2 g of 115% PPA).When dehydrochlorination is substantially complete, an additional 203.1g of P₂ O₅ is gradually added to the mixture and dissolved by stirringand heating essentially according to Example 27. The amount of P₂ O₅added is preselected (as determined in accord with the aforementionedformulae a* and b*) to provide the reaction mixture with an effective P₂O₅ content of approximately 88.2% prior to the start of polymerizationand an effective P₂ O₅ content of approximately 82.2% subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 18%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure: ##STR627## characterized by an intrinsicviscosity of 12 dL/g in MSA at 30° C.

Analogous to the foregoing Examples 26-30, other Type II extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Table 19. The e→denotes especially preferred selected monomer reactions.

                  TABLE 19                                                        ______________________________________                                        Polymers of Type II, Class 2                                                  Polymerization Reactions:                                                      ##STR628##                                                                    Monomer (3,2)                                                                                 ##STR629##                                                                             Polymer II(2)                                       ______________________________________                                         3f                                                                                            ##STR630##                                                                             [X] .sub.n                                           3g                                                                                            ##STR631##                                                                             [Y] .sub.n                                           3h                                                                                            ##STR632##                                                                             [TI] .sub.n                                          3i                                                                                            ##STR633##                                                                             [UI] .sub.n                                         ______________________________________                                    

EXAMPLE 31

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 99.923 g (0.35182 mol) of monomer 1c is dehydrochlorinated inan "initial" solution of 602.0 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 177.9 g of 85.4% H₃ PO₄ with 424.1 g of 115% PPA).When dehydrochlorination is substantially complete, 76.740 g (0.35182mol) of monomer 4a is added followed by the gradual addition of 272.7 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ added is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 84.4%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.0% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 10%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure: ##STR634##characterized by an intrinsic viscosity of 10 dL/g in MSA at 30° C.

Analogous to the foregoing Example 31, other Type III extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Table 20. The e→denotes especially preferred selected monomer reactions.

                  TABLE 20                                                        ______________________________________                                        Polymers of Type III, Class 1                                                 Polymerization Reactions:                                                      ##STR635##                                                                    ##STR636##                                                                    Monomer (1,1)                                                                           +     Monomer (4,1)                                                                             ##STR637##                                                                           Polymer III(1)                            ______________________________________                                         1c        +     4b                                                                                        ##STR638##                                                                           [B'A'F'Z] .sub.n                           1e        +     4a                                                                                        ##STR639##                                                                           [C'A'B'Z] .sub.n                           1e        +     4b                                                                                        ##STR640##                                                                           [C'A'F'Z] .sub.n                          ______________________________________                                    

EXAMPLE 32

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 109.94 g (0.27752 mol) of monomer 1l is dehydrochlorinated inan "initial" solution of 317.2 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 93.7 g of 85.4% H₃ PO₄ with 223.5 g of 115% PPA).When dehydrochlorination is substantially complete, 60.533 g (0.27752mol) of monomer 4a is added followed by the gradual addition of 219.5 gof P₂ O₅. The mixture is then stirred and heated essentially accordingto Example 8. The amount of P₂ O₅ added is preselected (as determined inaccord with the aforementioned formulae a* and b*) to provide thereaction mixture with an effective P₂ O₅ content of approximately 86.6%prior to the start of polymerization and an effective P₂ O₅ content ofapproximately 82.0% subsequent to substantial complete polymerization.The reaction product obtained exhibits stir-opalescence and is furthercharacterized as having a polymer concentration of 15%; fibers arereadily formed by direct spinning, or drawing from the reaction product.The polymer obtained is of the following structure: ##STR641##characterized by an intrinsic viscosity of 7 dL/g in MSA at 30° C.

Analogous to the foregoing Example 32, other Type III extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reactions in Table 21. The e→denotes especially preferred selected monomer reactions.

                  TABLE 21                                                        ______________________________________                                        Polymers of Type III, Class 2                                                 Polymerization Reactions:                                                      ##STR642##                                                                    ##STR643##                                                                    Monomer (1,2)                                                                           +     Monomer (4,1)                                                                             ##STR644##                                                                           Polymer III(2)                            ______________________________________                                         1l        +     4a                                                                                        ##STR645##                                                                           [D'A'B'Z] .sub.n                           1l        +     4b                                                                                        ##STR646##                                                                           [D'A'F'Z] .sub.n                           1p        +     4a                                                                                        ##STR647##                                                                           [E'A'B'Z] .sub.n                           1p        +     4b                                                                                        ##STR648##                                                                           [E'A'F'Z] .sub.n                          ______________________________________                                    

EXAMPLE 33

The procedure of Example 27 is essentially repeated. Instead of monomer3a, 117.5156 g (0.5149463 mol) of monomer 5a is dissolved in an"initial" solution of 623.7 g of PPA having a P₂ O₅ content of 77.0%(prepared by mixing 192.8 g of 85.4% H₃ PO₄ with 430.9 g of 115% PPA).When dissolution is substantially complete, an additional 257.8 g of P₂O₅ is gradually added to the mixture and dissolved by stirring andheating essentially according to Example 27. The amount of P₂ O₅ addedis preselected (as determined in accord with the aforementioned formulaea* and b*) to provide the reaction mixture with an effective P₂ O₅content of approximately 83.7% prior to the start of polymerization andan effective P₂ O₅ content of approximately 82.0% subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 10%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure: ##STR649## characterized by an intrinsicviscosity of 10 dL/g in MSA at 30° C.

EXAMPLE 34

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 70.784 g (0.28869 mol) of monomer 1a is dehydrochlorinated inan "initial" solution of 242.6 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 71.7 g of 85.4% H₃ PO₄ with 171.0 g of 115% PPA).When dehydrochlorination is substantially complete, 71.070 g (0.28869mol) of monomer 6a is added followed by the gradual addition of 162.9 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 86.4% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2 % subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 19%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure: ##STR650## characterized by an intrinsicviscosity of 7 dL/g in MSA at 30° C.

EXAMPLE 35

The procedure of Example 13 is essentially repeated. Instead of monomers1b and 2a, 67.798 g (0.31820 mol) of monomer 1b is dehydrochlorinated inan "initial" mixture of 343.3 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 101.4 g of 85.4% H₃ PO₄ with 241.9 g of 115% PPA).When dehydrochlorination is substantially complete, 78.336 g (0.31820mol) of monomer 6a is added followed by the gradual addition of 200.4 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 13. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 85.7% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2 % subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 15%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure: ##STR651## characterized by an intrinsicviscosity of 7 dL/g in MSA at 30° C.

EXAMPLE 36

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 90.945 g (0.32021 mol) of monomer 1c is dehydrochlorinated inan "initial" solution of 402.5 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 192.1 g of 85.4% H₃ PO₄ with 210.4 g of 115% PPA).When dehydrochlorination is substantially complete, 78.830 g (0.32021mol) of monomer 6a is added followed by the gradual addition of 307.8 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 84.9% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 12%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure: ##STR652## characterized by an intrinsic viscosityof 7 dL/g in MSA at 30° C.

Analogous to the foregoing Examples 34-36, other Type V extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Table 23. The e→denotes especially preferred selected monomer reactions.

                  TABLE 23                                                        ______________________________________                                        Polymers of Type V, Class 1                                                   Polymerization Reactions:                                                      ##STR653##                                                                    ##STR654##                                                                    Monomer (1,1)                                                                            +    Monomer (6,1)                                                                             ##STR655##                                                                           Polymer V(1)                              ______________________________________                                         1d        +     6a                                                                                        ##STR656##                                                                           [B'H'] .sub.n*                             1e        +     6a                                                                                        ##STR657##                                                                           [C'I'] .sub.n                              1f        +     6a                                                                                        ##STR658##                                                                           [C'H'] .sub.n                              1g        +     6a                                                                                        ##STR659##                                                                           [C'G'] .sub.n                              1h        +     6a                                                                                        ##STR660##                                                                           [B'M'] .sub.n                             ______________________________________                                         *Note: Oxygens always para on B'                                         

EXAMPLE 37

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 58.035 g (0.23669 mol) of monomer 1a is dehydrochlorinated inan "initial" solution of 307.7 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 90.9 g of 85.4% H₃ PO₄ with 218.8 g of 115% PPA).When dehydrochlorination is substantially complete, 76.281 g (0.23669mol) of monomer 6b is added followed by the gradual addition of 163.5 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 85.2% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2 % subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 17%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure: ##STR661## characterized by an intrinsicviscosity of 7 dL/g in MSA at 30° C.

EXAMPLE 38

The procedure of Example 13 is essentially repeated. Instead of monomers1b and 2a, 54.581 g (0.25617 mol) of monomer 1b is dehydrochlorinated inan "initial" solution of 330.4 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 97.6 g of 85.4% H₃ PO₄ with 232.7 g of 115% PPA).When dehydrochlorination is substantially complete, 82.559 g (0.25617mol) of monomer 6b is added followed by the gradual addition of 176.2 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 13. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 85.2% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2 % subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 16%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure: ##STR662## characterized by an intrinsicviscosity of 7 dL/g in MSA at 30° C.

EXAMPLE 39

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 73.126 g (0.25747 mol) of monomer 1c is dehydrochlorinated inan "initial" solution of 362.6 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 107.1 g of 85.4% H₃ PO₄ with 255.5 g of 115% PPA).When dehydrochlorination is substantially complete, 82.978 g (0.25747mol) of monomer 6b is added followed by the gradual addition of 185.5 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 85.0% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 15%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure: ##STR663## characterized by an intrinsic viscosityof 6 dL/g in MSA at 30° C.

Analogous to the foregoing Examples 37-39, other Type V extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration. P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Table 24a. Thee→ denotes especially preferred selected monomer reactions.

                  TABLE 24a                                                       ______________________________________                                        Polymers of Type V, Class 2                                                   Polymerization Reactions:                                                      ##STR664##                                                                    ##STR665##                                                                    Monomer (1,1)                                                                            +    Monomer (6,2)                                                                             ##STR666##                                                                           Polymer V(2)                              ______________________________________                                         1d        +     6b                                                                                        ##STR667##                                                                           [B'K'] .sub.n*                             1e        +     6b                                                                                        ##STR668##                                                                           [C'L'] .sub.n                              1f        +     6b                                                                                        ##STR669##                                                                           [C'K'] .sub.n                              1g        +     6b                                                                                        ##STR670##                                                                           [C'J'] .sub.n                              1h        +     6b                                                                                        ##STR671##                                                                           [B'N'] .sub.n                             ______________________________________                                         *Note: Oxygens always para on B'                                         

EXAMPLE 40

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 76.047 g (0.23369 mol) of monomer 1i is dehydrochlorinated inan "initial" solution of 369.2 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 109.1 g of 85.4% H₃ PO₄ with 260.1 g of 115% PPA).When dehydrochlorination is substantially complete, 58.269 g (0.23369mol) of monomer 6a is added followed by the gradual addition of 180.4 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 84.8% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2 % subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 15%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure: ##STR672## characterized by an intrinsicviscosity of 10 dL/g in MSA at 30° C.

EXAMPLE 41

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 74.075 g (0.25617 mol) of monomer 1j is dehydrochlorinated inan "initial" solution of 493.7 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 145.9 g of 85.4% H₃ PO₄ with 347.8 g of 115% PPA).When dehydrochlorination is substantially complete, 63.065 g (0.25617mol) of monomer 6a is added followed by the gradual addition of 221.2 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 84.3% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2 % subsequent tosubstantial complete polymerization. The reaction product obtainedexhibits stir-opalescence and is further characterized as having apolymer concentration of 12%; fibers are readily formed by directspinning, or drawing from the reaction product. The polymer obtained isof the following structure: ##STR673## characterized by an intrinsicviscosity of 6 dL/g in MSA at 30° C.

EXAMPLE 42

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 74.075 g (0.25617 mol) of monomer 1k is dehydrochlorinated inan "initial" solution of 493.7 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 145.9 g of 85.4% H₃ PO₄ with 347.8 g of 115% PPA).When dehydrochlorination is substantially complete, 63.065 g (0.25617mol) of monomer 6a is added followed by the gradual addition of 221.2 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 84.3% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 12%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure: ##STR674## characterized by an intrinsic viscosityof 6 dL/g in MSA at 30° C.

EXAMPLE 43

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 101.996 g (0.25747 mol) of monomer 1l is dehydrochlorinatedin an "initial" solution of 493.3 g of PPA having a P₂ O₅ content of77.3% (prepared by mixing 145.7 g of 85.4% H₃ PO₄ with 347.6 g of 115%PPA). When dehydrochlorination is substantially complete. 63.385 g(0.25747 mol) of monomer 6a is added followed by the gradual addition of221.5 g of P₂ O₅. The mixture is then stirred and heated according to aschedule similar to Example 8. The amount of P₂ O₅ added is preselected(as determined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 84.3% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 12%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure: ##STR675## characterized by an intrinsic viscosityof 7 dL/g in MSA at 30° C.

Analogous to the foregoing Examples 40-43, other Type V extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Tables 24b and24c. The e→ and p→ denote especially preferred and preferred selectedmonomer reactions respectively.

                  TABLE 24b                                                       ______________________________________                                        Polymers of Type V, Class 2                                                   Polymerization Reactions:                                                      ##STR676##                                                                    ##STR677##                                                                    Monomer (1,2)                                                                            +    Monomer (6,1)                                                                             ##STR678##                                                                           Polymer V(2)                              ______________________________________                                         1m        +     6a                                                                                        ##STR679##                                                                           [D'M'] .sub.n                              1n        +     6a                                                                                        ##STR680##                                                                           [E'G'] .sub.n                              1o        +     6a                                                                                        ##STR681##                                                                           [E'H'] .sub.n                              1p        +     6a                                                                                        ##STR682##                                                                           [E'I'] .sub.n                             ______________________________________                                    

                  TABLE 24c                                                       ______________________________________                                         Monomer (1,2)                                                                           +     Monomer (6,2)                                                                             ##STR683##                                                                           Polymer V(2)                              ______________________________________                                         1i        +     6b                                                                                        ##STR684##                                                                           [D'J'] .sub.n                              1j        +     6b                                                                                        ##STR685##                                                                           [D'K'] .sub.n*                             1k        +     6b                                                                                        ##STR686##                                                                           [D'K'] .sub.n**                            1l        +     6b                                                                                        ##STR687##                                                                           [D'L'] .sub.n                              1m        +     6b                                                                                        ##STR688##                                                                           [D'N'] .sub.n                              1n        +     6b                                                                                        ##STR689##                                                                           [E'J'] .sub.n                              1o        +     6b                                                                                        ##STR690##                                                                           [E'K'] .sub.n                              1p        +     6b                                                                                        ##STR691##                                                                           [E'L'] .sub.n                             ______________________________________                                         *Note: Oxygen always in 3,3'-position on                                      **Note: Oxygens always in 4,4'-positions on D'-                          

EXAMPLE 44

The procedure of Example 27 is essentially repeated. Instead of monomer3a, 123.074 g (0.64042 mol) of monomer 9a is dissolved in an "initial"solution of 423.1 g of PPA having a P₂ O₅ content of 77.3% (prepared bymixing 125.0 g of 85.4% H₃ PO₄ with 298.1 g of 115% PPA). Whendissolution is substantially complete, an additional 223.0 g of P₂ O₅ isgradually added to the mixture and dissolved by stirring and heatingessentially according to Example 27. The amount of P₂ O₅ added ispreselected (as determined in accord with the aforementioned formulae a*and b*) to provide the reaction mixture with an effective P₂ O₅ contentof approximately 85.1% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 13%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure: ##STR692## characterized by an intrinsic viscosityof 10 dL/g in MSA at 30° C.

EXAMPLE 45

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 86.502 g (0.30457 mol) of monomer 1c is dehydrochlorinated inan "initial" solution of 478.4 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 141.3 g of 85.4% H₃ PO₄ with 337.0 g of 115% PPA).

When dehydrochlorination is substantially complete, 79.864 g (0.30457mol) of monomer 7a is added followed by the gradual addition of 233.0 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 84.7% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 12%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure: ##STR693## characterized by an intrinsic viscosityof 10 dL/g in MSA at 30° C.

Analogous to the foregoing Example 45, other Type VII extended chainpolymers may be synthesized to yield liquid-crystalline compositionshaving varying proportions of polymer concentration, P₂ O₅ content andpolymer intrinsic viscosity in accordance with the present invention.

The synthesis is illustrated by the reaction systems in Tables 26 and27. The e→ denotes especially preferred selected monomer reactions.

                  TABLE 26                                                        ______________________________________                                        Polymers of Type VII, Class 1                                                 Polymerization Reactions:                                                      ##STR694##                                                                    ##STR695##                                                                    Monomer (1,1)                                                                           +     Monomer (7,1)                                                                             ##STR696##                                                                           Polymer VII(1)                            ______________________________________                                         1e        +     7a                                                                                        ##STR697##                                                                           [C'O'] .sub.n                             ______________________________________                                    

                  TABLE 27                                                        ______________________________________                                        Polymers of Type VII, Class 2                                                 Polymerization Reactions:                                                      ##STR698##                                                                    ##STR699##                                                                    Monomer (1,2)                                                                           +     Monomer (7,1)                                                                             ##STR700##                                                                           Polymer VII(2)                            ______________________________________                                         1l        +     7a                                                                                        ##STR701##                                                                           [D'O'] .sub.n                              1p        +     7a                                                                                        ##STR702##                                                                           [E'O'] .sub.n                             ______________________________________                                    

EXAMPLE 46

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 102.35 g (0.48036 mol) of monomer 1b is dehydrochlorinated inan "initial" solution of 329.2 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 97.3 g of 85.4% H₃ PO₄ with 231.9 g of 115% PPA).When dehydrochlorination is substantially complete, 67.296 g (0.48036mol) of monomer 8a is added followed by the gradual addition of 250.5 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 87.1% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 14%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure: ##STR703## characterized by an intrinsic viscosityof 7 dL/g in MSA at 30° C.

EXAMPLE 47

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 137.73 g (0.48494 mol) of monomer 1c is dehydrochlorinated inan "initial" solution of 370.8 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 109.6 g of 85.4% H₃ PO₄ with 261.3 g of 115% PPA).When dehydrochlorination is substantially complete, 67.939 g (0.48494mol) of monomer 8a is added followed by the gradual addition of 263.5 gof P₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 86.7% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 13%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure: ##STR704## characterized by an intrinsic viscosityof 7 dL/g in MSA at 30° C.

Analogous to the foregoing Examples 46 and 47, other Type VIII extendedchain polymers may be synthesized to yield liquid-crystallinecompositions having varying proportions of polymer concentration, P₂ O₅content and polymer intrinsic viscosity in accordance with the presentinvention.

The synthesis is illustrated by the reaction systems in Table 28. The e→and p→ denote especially preferred and preferred selected monomerreactions respectively.

                  TABLE 28                                                        ______________________________________                                        Polymers of Type VIII, Class 1                                                Polymerization Reactions:                                                      ##STR705##                                                                    ##STR706##                                                                    Monomer (1,1)                                                                           +     Monomer (8,1)                                                                             ##STR707##                                                                           VIII(1)Polymer                            ______________________________________                                         1a        +     8a                                                                                        ##STR708##                                                                           [B'R'] .sub.n                              1d        +     8a                                                                                        ##STR709##                                                                           [B'S'] .sub.n                              1e        +     8a                                                                                        ##STR710##                                                                           [C'Q'] .sub.n                              1f        +     8a                                                                                        ##STR711##                                                                           [C'S'] .sub.n                              1g        +     8a                                                                                        ##STR712##                                                                           [C'R'] .sub.n                              1h        +     8a                                                                                        ##STR713##                                                                           [B'U'] .sub.n                             ______________________________________                                    

EXAMPLE 48

The procedure of Example 8 is essentially repeated. Instead of monomers1a and 2a, 140.33 (0.35423 mol) of monomer 1l is dehydrochlorinated inan "initial" solution of 313.01 g of PPA having a P₂ O₅ content of 77.3%(prepared by mixing 92.5 g of 85.4% H₃ PO₄ with 220.5 g of 115% PPA).When dehydrochlorination is substantially complete, 49.627 g (0.35423mol) of monomer 8a is added followed by the gradual addition of 263.0 ofP₂ O₅. The mixture is then stirred and heated according to a schedulesimilar to Example 8. The amount of P₂ O₅ added is preselected (asdetermined in accord with the aforementioned formulae a* and b*) toprovide the reaction mixture with an effective P₂ O₅ content ofapproximately 85.8% prior to the start of polymerization and aneffective P₂ O₅ content of approximately 82.2% subsequent to substantialcomplete polymerization. The reaction product obtained exhibitsstir-opalescence and is further characterized as having a polymerconcentration of 14%; fibers are readily formed by direct spinning, ordrawing from the reaction product. The polymer obtained is of thefollowing structure: ##STR714## characterized by an intrinsic viscosityof 6 dL/g in MSA at 80° C.

EXAMPLE 49

A mixture of 123.38 g of 115% PPA and 52.63 g of concentratedorthophosphoric acid (85.7% H₃ PO₄) was stirred at 100° C. for 2h underreduced pressure. After allowing the solution to cool to 50° C. under aflow of argon, a portion (168.18 g) of the PPA (77.3% P₂ O₅) was addedunder a flow of argon to a resin kettle containing 57.61082 g (0.23496mol, a₁ =0.95) of 1a that had been prepared as described in Example 8and 2.6358 g (0.012371 mol, a₂ =0.05) of 1b that had been prepared bythe method of Wolfe and Arnold, Macromolecules, Vol. 14, 909 (1981) andrecrystallized from hydrochloric acid containing 3 wt % of stannouschloride. The mixture was then stirred at 50° C. for 33h under reducedpressure and 90° C. for 4 h under reduced pressure. Monomer 2a (41.0899g, 0.24733 mol=m, b₁ =1) was then added. The mixture was cooled toapproximately 40° C. and 139.18 g of P₂ O₅ was added to increase theeffective P₂ O₅ content before polymerization to 87.6%. The mixture wasthen stirred at the specified temperatures for the specified times undera flow of argon: 100° C. for 24h; 150° C. for 1h; 160° C. for 1h; 170°C. for 5.5h; and 200° C. for 64h. The final concentration of theresulting random copolymer was 16.8% in a PPA with an approximate P₂ O₅content of 82.5%. Fibers of the copolymer were isolated by drawing theresulting green, opalescent product and precipitating into water. Theintrinsic viscosity of the copolymer isolated after heating at 200° C.for 1.5h was shown to be 25.4 dL/g and actually decreased to 24.4 dL/gafter completing the above heating schedule. The copolymer obtainedapparently is of the following structure: ##STR715## where the molefraction of AI units (a₁ b₁) is believed to be 0.95, the mole fractionof BI units (a₂ b₁) is believed to be 0.05, the average block lengthsy₁₁ and y₂₁ are believed to be 20 and 1, respectively and the averagetotal number of recurring units of both types (n) is believed to beapproximately 100.

EXAMPLE 50

To a deaerated mixture of 16.09147 g (0.0656275 mol, a₁ =0.75) of 1a and4.66149 g (0.0218778 mol, a₂ =0.25) of 1b was added 220 g of freshlyprepared and deaerated PPA (The PPA was prepared from 173.81 g of 86.8%orthophosphoric acid and 267.64 g of phosphorus pentoxide, equilibrated,and deaerated). The mixture was stirred under an argon flow at: roomtemperature overnight; 50° C. for 3.5h; and 72° C. for 21h. The mixturewas stirred under reduced pressure at 72° C. overnight to substantiallycomplete dehydrochlorination. Terephthalic acid (2a) (14.53762 g,0.0875059 mol) was added to the solution and the mixture was deaeratedbefore stirring was initiated. The PPA prepared above was then added tothis mixture to give a total of 394.5 g of PPA. The slurry was thenstirred under reduced pressure for 0.5h at 110° C. and under an argonatmosphere at: 120° C. for 1h; 130° C. for 0.5h; 140° C. for 0.5h; 150°C. for 0.5h; 180° C. for 1.0h; 170° C. for 15.5h; 185° C. for 6.5h; and200° C. for 19h. The optically anisotropic product contained 5.3 wt %polymer in PPA (84.0% P₂ O₅ content). Precipitation of a small amount ofthe polymeric product provided the random copolymer, believed to havethe structure: ##STR716## where a₁ b₁ =0.75, y₁₁ =4, a₂ b₁ =0.25, andy₂₁ =1.33, with an intrinsic viscosity of 26.59 dL/g in MSA at 30° C.,which corresponds to an n value of approximately 110.

EXAMPLE 51

To a deaerated mixture of 22.36319 g (0.0912061 mol, a₁ =0.9) of 1a and2.15918 g (0.0101340 mol, a₂ =0.10) of 1b was added approximately 230 gof freshly prepared deaerated PPA. (The PPA was prepared by stirring amixture of 135.97 g of 85.4% orthophosphoric acid and 207.36 g ofphosphorus pentoxide at 150° C. overnight under an argon atmosphere,followed by deaeration by stirring under reduced pressure at 150° C. for5.5h. The solution was allowed to cool to room temperature under argonbefore use). The mixture was stirred under an argon flow at: roomtemperature overnight; 50° C. for 3h; and at 70° C. overnight. Thesolution was then stirred under reduced pressure for 2.5h at 70° C.Terephthalic acid (2a) (16.83595 g, 0.101340 mol); was added to thesolution and, after placing the kettle under reduced pressure, stirringwas initiated. The remaining shove-mentioned PPA was then added to themixture (total PPA added=317.6 g) under an argon atmosphere. Thepolymerization mixture was then stirred under an argon atmosphere at110° C. for 30 min; 120° C. for 30 min; 130° C. for 30 min; 140° C. for30 min; 150° C. for 30 min; 160° C. for 30 min; and 170° C. for 14.5h.The polymerization mixture was heated under an argon atmosphere withoutstirring at 185° C. for 5h and at 193°-200° C. for 28h. The finalpolymer concentration was 7.6 wt % in PPA (83.0% P₂ O₅). Precipitationof a small amount of the anisotropic polymer product provided the randomcopolymer of Type IX. Class 1 with the structure: ##STR717## where a₁ b₁=0.9, a₂ b₁ =0.10, and the average block lengths y₁₁ and y₂₁ arebelieved to be 10 and 1.11, respectively. The isolated copolymerpossessed an intrinsic viscosity of 26.36 dL/g in MSA at 30° C., whichcorresponds to an n value of approximately 110.

EXAMPLE 52

A solution of 135.51 g of 115% PPA and 59.10 g of 85.7% H₃ PO₄ wasstirred at 100° C. for 2h under reduced pressure. The solution wasallowed to cool to room temperature under reduced pressure, and 180.16 gof the mixture was added to 30.20054 g of 1a under an argon atmosphere.After a homogeneous mixture was obtained 28.29941 g (58.49995 g total,0.23859 mol total=m, a₁ =1) of deaerated 1a was added. The mixture wasstirred under reduced pressure at: 50° C. for 18.5h; 70° C. for 10 min;80° C. for 25 min; and 90° C. for 5.5h. Deaerated 2a (35.6892 g, 0.21482mol, b₁ =0.9) and 5.79905 g (0.02394 mol, b₂ =0.10) of deaerated4,4'-biphenyldicarboxylic acid (2aa) were added under an inertatmosphere. After the monomers were incorporated into the mixture, thereaction mixture was cooled to 40° C., and 136.11 g of deaerated P₂ O₅was added to give an effective P₂ O₅ content before polymerization of87.01%. After stirring at 100° C. for 63h, the polymerization wasstirred at: 160° C. for 2.5h; 170° C. for 5.5h, and 200° C. for 64h. Theconcentration of the resulting copolymer was 15.9% in PPA with a P₂ O₅content of approximately 82.5%. The reaction product was stir-opalescentand was drawn into oriented fibers. The copolymer possessed an intrinsicviscosity of 7.9 dL/g in MSA at 30° C. The structure of the resultingpolymer is believed to be: ##STR718## where a₁ b₁ is 0.9, a₁ b₂ is 0.1,y₁₁ is 10, y₁₂ is 1.1, and n is approximately 40.

EXAMPLE 53

A mixture of 20.10 g of concentrated orthophosphoric acid (85.7% H₃ PO₄)and 46.74 g of 115% PPA was stirred at 100° C. for 2h under reducedpressure in a 100 mL 3-necked flask. After allowing this PPA solution,having a P₂ O₅ content of 77.3%, to cool to 50° C. under reducedpressure, a portion (62.45 g) was added under a flow of argon to a 200mL resin kettle containing 20.2783 g (0.082703 mol=m, a₁ =1) of 1a thathad been prepared and deaerated as described in Example 7. The mixturewas then stirred at the specified temperatures for the specified timesunder either reduced pressure (vac) or argon flow (Ar): 50° C., 4h, vac;50° C., 15h, Ar; 80° C., 3h, vac; 80° C., 1h, vac; 90° C., 3h, vac; 80°C. 15h, Ar; 80° C., 7h, vac. Trans-1,2-cyclohexanedicarboxylic acid (2gg) (0.6781 g, 0.004132 mol, b₂ =0.05) that was obtained from AldrichChemical Company and was recrystallized from methanol before use wasadded to the kettle and then terephthalic acid (2a) (13.05455 g,0.078579 mol, b₁ =0.95) was added. Powdered P₂ O₅ (45.00 g) was thenadded to the mixture that had been cooled to 50° C. to increase theeffective P₂ O₅ content before polymerization to 86.8%. The mixture wasthen stirred for 17h at 100° C. under an argon flow.

The yellow mixture was then heated with stirring under argon as follows:120° C. for 1h; 130°-140° C. for 1h; 150° C. for 2h; 160° C. for 0.5h;170° C. for 4h (stir-opalescence was apparent during this time); 185° C.for 15.5h; and 200° C. for 75h. The final concentration of the resultingrandom copolymer was 16.4% in PPA, with a P₂ O₅ content of approximatelyof 82.2%. The polymer obtained apparently is of the following structure:##STR719## characterized as having an intrinsic viscosity inmethanesulfonic acid at 30° C. of 10.0 dL/g, which corresponds to anaverage n value of about 50, a mole fraction of --AI--_(n) units (a₁ b₁)of 0.95, and a mole fraction of --AA"--_(n) units (a₁ b₂) of 0.05. Theaverage block lengths, y₁₁ and y₁₂, are believed to be 20 and 1,respectively.

EXAMPLE 54

The procedure of Example 49 is essentially repeated. Instead of using 95mol % of monomer 1a, 5 mol % of monomer 1b, and 100 mol % of monomer 2a,a mixture of 50 mol % of monomer 1a and 50 mol % of monomer 1c issubstantially dehydrochlorinated in a comparable weight percent of PPAwith essentially similar P₂ O₅ content. After the addition of astoichiometric amount of monomer 2a and an appropriate amount of P₂ O₅(thereby raising the final P₂ O₅ content to substantially above about82%), the resultant mixture is then heated in essentially the samemanner in accordance with Example 12 to provide a copolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spinning, or drawing. The copolymer obtained is of thefollowing structure: ##STR720##

EXAMPLE 55

The procedure of Example 49 is essentially repeated. Instead of using 95mol % of monomer 1a, 5 mol % of monomer 1b, and 100 mol % of monomer 2a,a mixture of 50 mol % of monomer 1b and 50 mol % of monomer 1c issubstantially dehydrochlorinated in a comparable weight percent of PPAwith essentially similar P₂ O₅ content. After the addition of astoichiometric amount of monomer 2a and an appropriate amount of P₂ O₅(thereby raising the final P₂ O₅ content to substantially above about82%), the resultant mixture is then heated in essentially the samemanner in accordance with Example 12 to provide a copolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spinning, or drawing. The copolymer obtained is of thefollowing structure: ##STR721##

EXAMPLE 56

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1a is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 50 mol % of monomer 2a and 50 mol % of monomer 2jand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR722##

EXAMPLE 57

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1a is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 50 mol % of monomer 2a and 50 mol % of monomer 2kand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture isthen-heated in essentially the same manner in accordance with Example 12to provide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR723##

EXAMPLE 58

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1a is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 50 mol % of monomer 2a and 50 mol % of monomer 21and an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR724##

EXAMPLE 59

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 50 mol % of monomer 2a and 50 mol % of monomer 2jand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR725##

EXAMPLE 60

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 50 mol % of monomer 2a and 50 mol % of monomer 2kand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and cam bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR726##

EXAMPLE 61

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 50 mol % of monomer 2a and 50 mol % of monomer 21and an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR727##

EXAMPLE 62

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1a is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 75 mol % of monomer 2a and 25 mol % of monomer 2iand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR728##

EXAMPLE 63

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 75 mol % of monomer 2a and 25 mol % of monomer 2iand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR729##

EXAMPLE 64

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1c is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 75 mol % of monomer 2a and 25 mol % of monomer 2iand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR730##

EXAMPLE 65

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1a is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 75 mol % of monomer 2a and 25 mol % of monomer 2eand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR731##

EXAMPLE 66

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 75 mol % of monomer 2a and 25 mol % of monomer 2eand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR732##

EXAMPLE 67

The procedure of Example 49 is essentially repeated. Instead of using 95mol % of monomer 1a, 5 mol % of monomer 1b, and 100 mol % of monomer 2a,a mixture of 80 mol % of monomer 1a and 40 mol % of monomer 1i issubstantially dehydrochlorinated in a comparable weight percent of PPAwith essentially similar P₂ O₅ content. After the addition of astoichiometric amount of monomer 2a and an appropriate amount of P₂ O₅(thereby raising the final P₂ O₅ content to substantially above about82%), the resultant mixture is then heated in essentially the samemanner in accordance with Example 12 to provide a copolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spinning, or drawing. The copolymer obtained is of thefollowing structure: ##STR733##

EXAMPLE 68

The procedure of Example 49 was essentially repeated. Instead of using95 mol % of monomer 1a, 5 mol % of monomer 1b, and 100 mol % of monomer2a, a mixture of 80 mol % of monomer 1a and 20 mol % of monomer 11 wassubstantially dehydrochlorinated in a comparable weight percent of PPAwith essentially similar P₂ O₅ content. After the addition of astoichiometric amount of monomer 2a and an appropriate amount of P₂ O₅(thereby raising the final P₂ O₅ content to substantially above about82%), the resultant mixture was then heated in essentially the samemanner in accordance with Example 12 to provide a copolymerizationproduct. The product so formed was anisotropic-liquid crystalline(exhibited stir-opalescence) and was formed into ordered fibers bysimple drawing. The copolymer obtained is believed to be of thefollowing structure: ##STR734##

EXAMPLE 69

The procedure of Example 49 is essentially repeated. Instead of using 95mol % of monomer 1a, 5 mol % of monomer 1b, and 100 mol % of monomer 2a,a mixture of 85 mol % of monomer 1c and 15 mol % of monomer 11 issubstantially dehydrochlorinated in a comparable weight percent of PPAwith essentially similar P₂ O₅ content. After the addition of astoichiometric amount of monomer 2a and an appropriate amount of P₂ O₅(thereby raising the final P₂ O₅ content to substantially above about82%), the resultant mixture is then heated in essentially the samemanner in accordance with Example 12 to provide a copolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spinning, or drawing. The copolymer obtained is of thefollowing structure: ##STR735##

EXAMPLE 70

The procedure of Example 52 is essentially repeated. Instead of using100 mol % of monomer 1a, 90 mol % of monomer 2a, and 10 mol % of monomer2aa, 100 mol % of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 96 mol % of monomer 2a and 5 mol % of monomer 2aaand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR736##

EXAMPLE 71

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1b is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 95 mol % of monomer 2a and 5 mol % of monomer 2 ggand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR737##

EXAMPLE 72

The procedure of Example 53 is essentially repeated. Instead of using100 mol % of monomer 1a, 95 mol % of monomer 2a, and 5 mol % of monomer2 gg, 100 mol % of monomer 1a is substantially dehydrochlorinated in acomparable weight percent of PPA with essentially similar P₂ O₅ content.After the addition of 95 mol % of monomer 2a and 5 mol % of monomer 2ffand an appropriate amount of P₂ O₅ (thereby raising the final P₂ O₅content to substantially above about 82%), the resultant mixture is thenheated in essentially the same manner in accordance with Example 12 toprovide a copolymerization product. The product so formed isanisotropic-liquid crystalline (exhibits stir-opalescence) and can bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is of the following structure: ##STR738##

EXAMPLE 73

Two polymerizations (Step A and Step B) were conducted simultaneously inseparate resin kettles and combined at a later stage (Step C) to give aproduct of a block copolymer believed to have the following structure:##STR739## where a₁ b₁ is 0.793 and a₁ b₂ is 0.207 and y₁₁ is greaterthan about 30.

Step A: Preparation of --AI--_(n). A mixture of 92.06 g of 115% PPA and39.45 g of concentrated orthophosphoric acid (85.7% H₃ PO₄) was stirredat 100° C. for 2h under reduced pressure. A portion (128.63 g) of thehot PPA (77.3% P₂ O₅) was added under a flow of argon to a resin kettlecontaining 41.42682 g (0.16896 mol) of 1a. The mixture was stirred at50° C. under argon flow for 15h, then under reduced pressure at 60° C.for 23.5h, 70° C. for 6h, and 80° C. for 8.5h to effectdehydrochlorination. Terephthalic acid (2a) (28.0688 g, 0.16895 mol) wasthen added in four portions. The mixture was cooled to approximately 40°C., and 92.22 g of P₂ O₅ was added. The mixture was stirred at thefollowing temperatures for the specified times under a flow of argon:100° C. for 42.5h; 120° C. to 160° C. in increments of 10° C. per 0.5h;170° C. for 2.5h. At this time the mixture became stir-opalescent and asample of the dope exhibited birefringence under plane-polarized light.After an additional 3h at 170° C. the polymer from Step B was added (SeeStep C). The intrinsic viscosity of Polymer --AI--_(n) isolated from thereaction mixture immediately before Step C was 2.3 dL/g whichcorresponds to an n value (average number of recurring units) of 30 anda p value (extent reaction) of 0.983.

Step B: Preparation of --AG"--_(n). A mixture of 30.72 g of 115% PPA and13.13 g of concentrated orthophosphoric acid (85.7% H₃ PO₄) was stirredat 100° C. for 2h under reduced pressure. The PPA (41.66 g; 77.3% P₂ O₅)was added without cooling under a flow of argon to a resin kettlecontaining 13.80877 g (0.05632 mol) of 1a. The mixture was stirred at50° C. under argon flow for 15h, then under reduced pressure a 86° C.for 23.5h, 70° C. for 6h, and 80° C. for 35.5h. Isophthalic acid (2ss)(9.3569 gg, 0.05632 mol) that had been obtained from Aldrich ChemicalCompany in 99% purity was twice recrystallized from 90% aqueous ethanoland dried at 110° C. for 24h and was then added in two portionsincorporating the solid after each addition. The mixture was cooled toapproximately 40° C., and then 31.59 g of P₂ O₅ was added. The mixturewas then heated simultaneously and at the same heating schedule as thesolution in Step A.

Step C: Block Copolymeriztion. After 5.5h at 170° C., 72 g of theviscous, red, optically isotropic product from Step B was added to thekettle from Step A under an argon atmosphere at the time indicated inStep A. Both kettles were heated under an argon flow as follows: 170° C.for 12.8h; 190° C. for 2h; 200° C. for 26h. The resulting mixtureremained stir-opalescent and continued to polymerize as indicated byintrinsic viscosities of samples removed at various times. Uponprecipitation in H₂ O, the final sample of the resulting copolymer hadan intrinsic viscosity of 17.5 dL/g in MSA at 30° C. The finalprecipitated sample of the portion of the product from Step B that hadnot been added to the product from Step A (but had been heated accordingto the same schedule as the mixture) had an intrinsic viscosity of 1.8dL/g in MSA at 30° C. The weight percent of polymer --AI--_(n) in theproduct from Step A was 16.2; the weight percent of polymer --AG"--_(n)in the product from Step B was 16.3. The weight percent of blockcopolymer ##STR740## was therefore calculated to be 16.2; the weightpercents of the individual --AI--_(n) and --AG"--_(n) segments of theblock copolymer in the final product were 12.9 and 3.4, respectively, ascalculated from the weights of the constituent polymers added and thetotal weight of the resulting product. The mol percent of mesogenic--AI--_(n) and flexible --AG"--_(n) units were 79.3 and 20.7,respectively, as calculated from the weights of the constituent polymersadded.

EXAMPLE 74

Two polymerizations were conducted simultaneously in separate resinkettles (Steps A and B), and combined at a later stage (Step C) to givea block polymer product believed to have the following structure:##STR741## where a₁ b₁ is 0.587 and a₁ b₂ is 0.413 and Y₁₁ is greaterthan about 40.

Step A: Preparation of --AI--_(n). A mixture of 36.73 g of 115% PPA and24.43 g of concentrated orthophosphoric acid (85.0% H₃ PO₄) was stirredat 100° C. for 4.5h under reduced pressure. A portion (58.69%) of thehot PPA (74.9% P₂ O₅) was added under a flow of argon to a resin kettlecontaining 20.71434 g (0.08448 mol) of 1a. The mixture was stirred underreduced pressure at 50° C. for 1h, 70° C. for 1.3h, and 80° C. for 23h.To dissolve monomer, 6.02 g of P₂ O₅ was added, and the kettle washeated at 80° C. for an additional 26h. Terephthalic acid (2a) (14.0351g, 0.08448 mol) was then added in three portions. The acid monomer wasincorporated by stirring after each addition. The kettle was cooled to50° C. and an additional 48.24 g deaerated P₂ O₅ was added. The mixturewas stirred under argon flow at the following temperatures for thespecified times: 100° C. for 18h; 150° C. for 2h; 170° C. for 5h. (After1h at 170° C. the mixture exhibited stir-opalescence). At this time thepolymer from Step B was added. (See Step C).

Step B: Preparation of --AN"--_(n) A mixture of 63.88 g of 115% PPA and42.51 g of concentrated orthophosphoric acid (85.0% H₃ PO₄) was stirredat 100° C. for 4.5h under reduced pressure. A portion (104.41 g) of thePPA (74.9% P₂ O₅) was added without cooling under a flow of argon to aresin kettle containing 20.26865 g (0.08266 mol) of 1a. The mixture wasstirred under reduced pressure at 80° C. for 0.8h, 60° C. for 7.5h, and80° C. for 9.5h. Sebacic acid, (monomer 2zz, purified by crystallizationof the disodium salt, then repeated recrystallization of the free acidin H₂ O and dried in vacuo at 80° C. for 24h) (16.7190 g, 0.08266 mol),was then added in three portions to the resin kettle, incorporatingafter each addition. The mixture was cooled to 50° C. and 70.91 g of P₂O₅ was added slowly. The polymerization proceeded rapidly, and thegel-like solid was heated without stirring at 100° C. for 16.5h and at130° C. for 7.8h. At this time the polymer was removed in an inertatmosphere, leaving a portion in the kettle which was reassembled andheated according to the same schedule as the block copolymer.

Step C: Block Copolymerization. A portion of the polymer from Step B(153.13 g) was added under an argon atmosphere to the kettle from StepA. The mixture was then stirred under argon flow at 170° C. for 16h andat 200° C. for 28h. The mixture remained stir-opalescent and continuedto polymerize as shown by an increase in the bulk viscosity. The weightpercent of polymer --AI--_(n) in the product from Step A was 16.1; theweight percent of polymer --AN"--_(n) in the product from Step B was12.1. The weight percent of block copolymer was calculated to be 12.1;the weight percents of --AI--_(n) and --AN"--_(n) segments of the blockcopolymer in solution were 6.8 and 5.6 respectively. The mole percent ofmesogenic --AI--_(n) and --AN"--_(n) units were 58.7 and 41.3respectively, as calculated from the weights of the constituent polymersadded. The resulting polymer isolated was not completely soluble inmethane sulfonic acid thus precluding intrinsic viscosity measurements.

EXAMPLE 75

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 13 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 3:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR742##

EXAMPLE 76

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 13 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR743##

EXAMPLE 77

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 13 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:3. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR744##

EXAMPLE 78

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 13 are diverted into a common,agitated reaction vessel in amounts to give a ratio of 1:4. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR745##

EXAMPLE 79

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 28 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR746##

EXAMPLE 80

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 13 and 28 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR747##

EXAMPLE 81

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 16 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR748##

EXAMPLE 82

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 17 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR749##

EXAMPLE 83

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 18 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR750##

EXAMPLE 84

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 13 and 17 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR751##

EXAMPLE 85

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 19 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR752##

EXAMPLE 86

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 22 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR753##

EXAMPLE 87

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 28 and 22 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR754##

EXAMPLE 88

The procedure of Example 73 is essentially repeated. Instead of usingmonomers 1a and 2ss in Step B, equimolar quantities of monomers 1a and2ff are polymerized at a comparable concentration and to a comparableextent of reaction. The (partially completed) separate polymerizationproducts (i.e., homo-oligomers) from Steps A and B are diverted into acommon agitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR755##

EXAMPLE 89

The procedure of Example 73 is essentially repeated. Instead of usingmonomers 1a and 2ss in Step B, equimolar quantities of monomers 1a and2xx are polymerized at a comparable concentration and to a comparableextent of reaction. The (partially completed) separate polymerizationproducts (i.e., homo-oligomers) from Steps A and B are diverted into acommon agitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR756##

EXAMPLE 90

The procedure of Example 73 is essentially repeated. Instead of usingmonomers 1a and 2ss in Step B, equimolar quantities of monomers 1a and2uu are polymerized at a comparable concentration and to a comparableextent of reaction. The (partially completed) separate polymerizationproducts (i.e., homo-oligomers) from Steps A and B are diverted into acommon agitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR757##

EXAMPLE 91

The procedure of Example 73 is essentially repeated. Instead of usingmonomers 1a and 2ss in Step B, equimolar quantities of monomers 1q and2a are polymerized at a comparable concentration and to a comparableextent of reaction. The (partially completed) separate polymerizationproducts (i.e., homo-oligomers) from Steps A and B are diverted into acommon agitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR758##

EXAMPLE 92

The procedure of Example 73 is essentially repeated. Instead of usingmonomer 1a in Step A, an equimolar quantity of 1b is used. Instead ofusing monomers 1a and 2ss in Step B, equimolar quantities of monomers 1band 2ss are polymerized at a comparable concentration and to acomparable extent of reaction. The (partially completed) separatepolymerization products (i.e., homo-oligomers) from Steps A and B arediverted into a common agitated reaction vessel in amounts to give aratio of 1.5:1. The polymerization of the resultant mixture is allowedto continue to form a substantially polymerized blockpolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spinning or drawing and the like. The blockpolymerobtained is of the following structure: ##STR759##

EXAMPLE 93

The procedure of Example 73 is essentially repeated. Instead of usingmonomer 1% in Step A, an equimolar quantity of 1b is used. Instead ofusing monomers 1a and 2ss in Step B, equimolar quantities of monomers 1band 2xx are polymerized at a comparable concentration and to acomparable extent of reaction. The (partially completed) separatepolymerization products (i.e., homo-oligomers) from Steps A and B arediverted into a common agitated reaction vessel in amounts to give aratio of 2:1. The polymerization of the resultant mixture is allowed tocontinue to form a substantially polymerized blockpolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spinning or drawing and the like. The blockpolymerobtained is of the following structure: ##STR760##

EXAMPLE 94

The procedure of Example 73 is essentially repeated. Instead of usingmonomer 1a in Step A, an equimolar quantity of 1b is used. Instead ofusing monomers 1a and 2ss in Step B, equimolar quantities of monomers 1band 2zz are polymerized at a comparable concentration and to acomparable extent of reaction. The (partially completed) separatepolymerization products (i.e., homo-oligomers) from Steps A and B arediverted into a common agitated reaction vessel in amounts to give aratio of 2:1. The polymerization of the resultant mixture is allowed tocontinue to form a substantially polymerized blockpolymerizationproduct. The product so formed is anisotropic-liquid crystalline(exhibits stir-opalescence) and can be directly utilized for forminginto articles by spinning or drawing and the like. The blockpolymerobtained is of the following structure: ##STR761##

EXAMPLE 95

The procedure of Example 27 is essentially repeated. Instead of usingmonomer 3a, a mixture of 80 mol % of monomer 3a and 20 mol % of monomer3c is substantially dehydrochlorinated in a comparable weight percent ofPPA with essentially similar P₂ O₅ content. After the addition ofappropriate amount of P₂ O₅ (thereby raising the final P₂ O₅ content tosubstantially above about 82%), the resultant mixture is then heated inessentially the same manner in accordance with Example 27 to provide acopolymerization product. The product so formed is anisotropic-liquidcrystalline (exhibits stir-opalescence) and can be directly utilized forforming into articles by spinning, or drawing. The copolymer obtained isof the following structure: ##STR762##

EXAMPLE 96

The procedure of Example 27 is essentially repeated. Instead of usingmonomer 3a, a mixture of 80 mol % of monomer 3a and 20 mol % of monomer3d is substantially dehydrochlorinated in a comparable weight percent ofPPA with essentially similar P₂ O₅ content. After the addition ofappropriate amount of P₂ O₅ (thereby raising the final P₂ O₅ content tosubstantially above about 82%), the resultant mixture is then heated inessentially the same manner in accordance with Example 27 to provide acopolymerization product. The product so formed is anisotropic-liquidcrystalline (exhibits stir-opalescence) and can be directly utilized forforming into articles by spinning, or drawing. The copolymer obtained isof the following structure: ##STR763##

EXAMPLE 97

The procedure of Example 27 was essentially repeated. Instead of usingmonomer 3a, a mixture of 80 mol % of monomer 3a and 20 mol % of monomer3e was substantially dehydrochlorinated in a comparable weight percentof PPA with essentially similar P₂ O₅ content. After the addition ofappropriate amount of P₂ O₅ (thereby raising the final P₂ O₅ content tosubstantially above about 82%), the resultant mixture was then heated inessentially the same manner in accordance with Example 27 to provide acopolymerization product. The product so formed was anisotropic-liquidcrystalline (exhibits stir-opalescence), highly drawable, and could bedirectly utilized for forming into articles by spinning, or drawing. Thecopolymer obtained is believed to be of the following structure:##STR764##

EXAMPLE 98

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 27 and 29 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR765##

EXAMPLE 99

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 27 and 30 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR766##

EXAMPLE 100

3,4-diaminobenzoic acid (3e) (Aldrich, 97%) was recrystallized from hotwater with 3-4 g of carbon black and 0.5 g of sodium dithionite addedfor every 30 g of 3e. The recovered light orange crystals were dried atroom temperature under reduced pressure for 24h. An acid mixtureprepared from 183.4 g of 115% PPA and 78.6 g of 85.7% H₃ PO₄ (J. T.Baker Analyzed Reagent) was deaerted by heating in a 3-necked flask at100° C. for 2h under reduced pressure and then at 50° C. under reducedpressure for 17h. To a 500 mL resin kettle was added 20.24 g of 3e. Thekettle was then deaerated by applying reduced pressure and then fillingwith nitrogen three times. 51.11 g of the above-mentioned PPA was addedto the kettle and the contents stirred until well mixed. 38.77 g of P₂O₅ (J. T. Baker Analyzed Reagent, 99.1%) was added. The temperature ofthe kettle was raised to 100° C. and the P₂ O₅ incorporated into themixture. The following heating schedule was used with color changes asnoted: 100° C. for 20 min; 110° C. for 20 min; 120° C. for 20 min; 130°C. for 20 min; color changed from tan to green; 140° C. for 20 min; thegreen color became darker. Reduced pressure was briefly applied whichcaused considerable foaming; 105° C. for 20 min; 160° C. for 20 min. Asample was removed and precipitated in water to give a red polymericsubstance with an intrinsic viscosity in MSA at 30.0° C. of 4.25 dL/g.Heating at 160° C. was continued for another 30h. The intrinsicviscosity in MSA at 30° C. of polymer component of a sample removed atthis time was measured to be 4.5 dL/g. The reaction was heated at 175°C. an additional 35h. The resultant red-brown polymeric materialisolated from this solution had an intrinsic viscosity of 4.5 dL/g inmethanesulfonic acid at 30.0° C. Final reaction product contained 16.8%of polymer --W--_(n) in PPA. Initial P₂ O₅ content was 77.3%, final P₂O₅ content was 82.2%.

EXAMPLE 101

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 27 and 100 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR767##

EXAMPLE 102

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 27 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:3. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR768##

EXAMPLE 103

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 26 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR769##

EXAMPLE 104

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 13 and 27 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:4. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR770##

EXAMPLE 105

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 13 and 26 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR771##

EXAMPLE 106

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 30 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR772##

EXAMPLE 107

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 30 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 3:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR773##

EXAMPLE 108

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 13 and 30 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:3. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR774##

EXAMPLE 109

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 13 and 30 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR775##

EXAMPLE 110

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 8 and 100 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR776##

EXAMPLE 111

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 13 and 100 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1.5:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR777##

EXAMPLE 112

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 28 and 100 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 2:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR778##

EXAMPLE 113

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 19 and 27 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR779##

EXAMPLE 114

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 23 and 27 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:1. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR780##

EXAMPLE 115

The procedure of Example 73 is essentially repeated. Subsequent to thestart of polymerization and at a preselected range of intrinsicviscosities or after a predetermined selected temperature and rate ofreaction, the (partially completed) separate polymerization products(i.e., homo-oligomers) of Examples 22 and 27 are diverted into a commonagitated reaction vessel in amounts to give a ratio of 1:2. Thepolymerization of the resultant mixture is allowed to continue to form asubstantially polymerized blockpolymerization product. The product soformed is anisotropic-liquid crystalline (exhibits stir-opalescence) andcan be directly utilized for forming into articles by spinning ordrawing and the like. The blockpolymer obtained is of the followingstructure: ##STR781##

EXAMPLE 116

A mixture of 42.13 g of PPA (83.8% P₂ O₅) and 18.06 g of H₃ PO₄ (85.9%)was stirred and heated to 100° C. in a 100 ml 3-necked flask. The flaskwas placed under reduced pressure overnight. 21.34 g of3,4-diaminobenzoic acid.2 HCl was added to a 100 ml resin kettle. Theresin kettle was deaerated and flushed with argon and 42.81 g of theabove prepared PPA solvent with a P₂ O₅ content of 77.32% was then addedto the kettle. The flask was heated with an oil bath at 55° C. with slowstirring under a water aspirator (reduced pressure) for 0.33 hours. Theflask was then placed under vacuum for an additional 45.87 hours. Duringthe initial 5 hours of dehydrochlorination, the temperature wasincreased from 55° C. to 70° C. Near the end of the dehydrochlorination,the mixture changed from a very pale pink to a blue-green color that wasalmost transparent. 26.56 g of deaerated P₂ O₅ was added as a powderunder argon flow. The P₂ O₅ was incorporated using a combination ofstirring and vacuum at about 70° C. The mixture was allowed toequilibrate at 100° C. with stirring under argon flow for 17.33 hours.The amount of P₂ O₅ added was calculated to provide the reaction mixturewith an effective P₂ O₅ content of approximately 86% prior to thebeginning of polymerization and an effective P₂ O₅ content ofapproximately 81.97% subsequent to substantial complete polymerization.The mixture was heated to a final temperature of 200° C. following theheating schedule outlined below.

    ______________________________________                                        Temperature                                                                              Time                                                               (°C.)                                                                             (Hours)    Observations                                            ______________________________________                                        110        0.33       Dark mint green; creamy.                                120        0.67       Less viscous.                                           130        0.38                                                               140        0.70       More viscous (mixture full                                                    of bubbles).                                            150        0.63       Darker green; shiny glass-                                                    like appearance.                                        160        0.48       Mixture riding on stir blades.                          170        0.55       Unable to stir fast; darker                                                   green.                                                  185        2.43       Mixture more transparent                                200        19.15                                                              ______________________________________                                    

The reaction product obtained is optically isotropic characterized ashaving a polymer concentration of 13.14% and an intrinsic viscosity of6.57 dL/g in MSA at 30° C. The polymer obtained is of the followingstructure: ##STR782##

EXAMPLE 117

The reaction product of Example 13 was placed in a constant displacementspinning apparatus and extruded at about 3.4 MPa (500 psi) through a0.381 mm (0.015 in.) diameter orifice and passed through a 20.96 cm(8.25 in.) air gap at a selected take up rate to give a spin draw ratioof about 6.12:1. The extrusion temperature was about 63° C. Thecoagulation medium was water. The average tensile properties of sevensingle filaments (ASTHD 3379, 2.54 cm (1.0 in.) gage length) were 2.96GPa (4.3×10⁵ psi) tensile strength, 89.6 GPa (13×10⁶ psi) modulus, andelongation at break range from 4.2-6%. The fiber diameters ranged from33-37 micrometer (0.00129 to 0.00146 inches). Heat created filaments(conditioned under tension at 500° C. for 60 seconds in a nitrogenatmosphere) gave average values of tensile strength 3.45 GPa (5.0×10⁵psi), modulus 317 GPa (46×10⁶ psi), and elongation at break 1.8-2.4%.The heat treated fiber diameters ranged from 29.7-33.3 micrometer(0.00117 to 0.00133 inches).

EXAMPLE 118

The procedure of Example 13 was essentially repeated using 21.0018 g(0.09857 mol) of 1b and 16.3768 g (0.09858 mol) of 2a. The P₂ O₅ contentduring dehydrochlorination was 75.16% for 8 hours and was increased to81.37% by the addition of deaerated P₂ O₅ for an additional 24 hours.The concentration of monomer 1b during dehydrochlorination was initially21.94%. After the addition of 2a, P₂ O₅ was added so as to raise the P₂O₅ content to 87.5% before polymerization and to give a P₂ O₅ contentafter substantial polymerization of 83.17%. The mixture was then heatedat 185° C. for 28 hours. The concentration of polymer --BI--_(n) was13.8 weight percent. The isolated polymer --AI--_(n) had an intrinsicviscosity of 24.4 dL/g.

EXAMPLE 119

The reaction product from Example 118 was dry-jet-wet spun as in Example117 except that the extrusion temperature was 70° C., the jet diameterwas 0.254 mm (0.010 in.), the air gap was 20.3 cm (8 in.) and therequired extrusion pressure was 1.17 MPa (170 psi). The average tensilestrength of nine single filaments was 3.12 GPa (453,000 psi) whichranged from about 2.82 to about 3.35 GPa (410,000 to 486,000 psi). Theaverage tensile modulus was 303 GPa (43.9×10⁶ psi). After treating thisfiber at 450° C. in air for 30 seconds with a 2% stretch the strengthwas unchanged and the modulus had increased to an average of 410 GPa(59.5×10⁶ psi). Repeating these conditions with a 2.8% stretch gaveidentical strength and a modulus of 394 GPa (57.09×10⁶ psi). Aftertreating the as spun fiber at 500° C. in air for 30 seconds with a 2.5%stretch the tensile strength increased to an average of 3.58 GPa(519,000 psi) and the modulus increased to 467 GPa (67.8×10⁶ psi).

EXAMPLE 120

A mixture of 13.35 g of 115% PPA and 8.89 g of 85.9% H₃ PO₄ was stirredunder reduced pressure for 3.3 h at 100° C. To a 100-mL resin kettle wasadded 17.76096 g (0.09368 mol) of 3-amino-4-hydroxybenzoic acidhydrochloride (3d). The kettle was flushed with argon, and 20.45 g ofthe above PPA (P₂ O₅ content=75.2%) was added. This mixture was stirredunder reduced pressure; however, the mixture solidified overnight. 115%PPA (8.20 g, P₂ O₅ content=83.8%) was added to obtain a stirrablemixture with a P₂ O₅ content of 77.6%. After 8 h, 10.17 g of P₂ O₅ wasadded as a powder, giving a P₂ O₅ content of 83.49%. Dehydrochlorinationwas substantially complete after stirring for an additional 15 h at 80°C. Additional P₂ O.sub. 5 (12.65 g) was then added at 100° C. inaccordance with equation b* to give an f of 82.2% and an intermediate P₂O₅ content of 87.55%. The kettle was placed under reduced pressurebefore incorporating the P₂ O₅ by stirring. The mixture was then stirredfor 2.4 h at 100° C., and the temperature was increased to 140° C. After1 h at this temperature, a clear amber solution was obtained. Thetemperature was raised to 150° C. for 1 h and then raised to 185° C.After 1 h at 185° C., the reaction mixture shoved a tan pearlescencewhen stirred and was birefringent when viewed at rest under crossedpolars. The reaction mixture yes then heated at 185° C. for anadditional 40 h. Nearly colorless, high strength fibers were readilyformed by drawing the reaction product. The concentration of polymer--V--_(n) in the product was calculated to be 16.67%. The intrinsicviscosity of polymer --V--_(n) isolated from the product was measured tobe 13.84 dL/g in MSA at 30° C. The dried polymer had a TGA break in airat 10° C./min of 640° C. Anal. Calcd. for C₇ H₃ NO: C, 71.80; H, 2.58;N, 11.96. Found: C, 71.09; H, 2.64; N, 11.67; Residue, 0.8.

EXAMPLE 121

The reaction mixture of Example 120 was placed in a constantdisplacement spinning apparatus and extruded at about 3.4 HPa (500 psi)through a 0.381 mm (0.015 in.) diameter orifice into a 31.75 cm (12.5in.) air gap with a take-up rate to supply a spin draw ratio of 6.6:1.The temperature of the spinning dope was 65° C. The as spun fiber was ofpoor quality and very non-uniform. The as-spun properties were (340×10³psi) tensile strength, 41.3-96.5 GPa (6-14×10⁶ psi) modulus, with noelongation to break determined. After heat treatment under tension at500° C. for 60 seconds in nitrogen, the strength was essentially.unchanged and the modulus had increased to an average value of 136 GPa(19.7×10⁶ psi).

EXAMPLE 122

The procedure of Example 120 was essentially repeated using 80.95 g(0.4269 mol) of monomer 3d, 34.37 g of 85.9% H₃ PO₄, 80.13 g of 115% PPAand 118.06 g of P₂ O₅. These amounts gave a m_(o) of 77.32%, anintermediate P₂ O₅ content of 88.83%, and (because of the loss of 1.54 gof water during polycondensation) an _(f) of 83.8%. The P₂ O₅ contentprofile for this example is graphically presented by the step-wise curveof FIG. 13. The concentration of polymer --V--_(n) in the reactionproduct was calculated to be 16.87 weight %. The total reaction timeabove 100° C. was 43.5 hours. The stir-opalescent reaction product wasbirefringent at rest and gave colorless fibers after drawing andprecipitating in water. The intrinsic viscosity of isolated polymer--V--_(n) was 12.0 dL/g.

EXAMPLE 123

The reaction product of Example 122 was placed in a constantdisplacement spinning apparatus and extruded at about 3.4 MPa (500 psi)through a 0.25 mm (0.010 in.) diameter orifice into a 20.3 cm (8 in.)air gap with a take up race to supply a spin draw ratio of 145:1. Thetemperature of the spinning dope was 90° C. The tensile strength offibers (average of nine breaks) spun from said dope was 3.57 GPa(518,000 psi). One of the fibers tested gave a break value of 5.01 GPa(727,000 psi). The average tensile modulus was 133 GPa (19.3×10⁶ psi).This value does not take into account the machine compliance. Theaverage strain at break was 3.3%. The fiber diameter was 16 micrometer(0.63×10⁻³ in.).

EXAMPLE 124

The reaction product of Example 122 was placed in a constantdisplacement spinning apparatus and extruded at about 3.4 MPa (500 psi)through a 0.250 mm (0.010 in.) diameter orifice into a 20.3 cm (8.0 in.)air gap with a take up race to supply a spin draw ratio of 125:1. Thetemperature of the spinning dope was 90° C. The tensile strength offibers (average of ten breaks) spun from said dope was 2.57 GPa (373,000psi). One of the fibers tested gave a break value of 3.38 GPa (491,000psi). The average tensile modulus was 79 GPa (11.5×10⁶ psi). This valuedoes not take into account the machine compliance. The average strain atbreak was 4.6%. The fiber diameter was 19 micrometer (0.748×10⁻³ in.).

EXAMPLE 125

The reaction product of Example 122 was placed in a constantdisplacement spinning apparatus and extruded at about 3.4 MPa (500 psi)through a 0.25 mm (0.010 in.) diameter orifice into a 20.3 cm (8.0 in.)air gap with a take up rate to supply a spin draw ratio of 100:1. Thetemperature of the spinning dope was 90° C. The tensile strength offibers (average of seven breaks) spun from said dope was 2.83 GPa(410,000 psi). One of the fibers tasted gave a break value of 3.29 GPa(491,000 psi). The average tensile modulus was 61 GPa (8.8×10⁶ psi).This value does not take into account the machine compliance. Theaverage strain at break was 4.8%. The fiber diameter was 21 micrometer(0.827×10⁻³ in.).

EXAMPLE 126

The reaction product of Example 122 was placed in a constantdisplacement spinning apparatus and extruded at about 3.4 MPa (500 psi)through a 0.025 mm (0.010 in.) diameter orifice into a 20.3 cm (8.0 in.)air gap with a take up rate to supply a spin draw ratio of 17.2:1. Thetemperature of the spinning dope was 80° C. The tensile strength offibers (average of seven breaks) spun from said dope was 2.76 GPa(400,000 psi). The average tensile modulus was 41GPa (6.0×10⁶ psi). Thisvalue does not take into account the machine compliance. The fiberdiameter was 45 micrometer (1.76×10⁻³ in.).

EXAMPLE 127 Poly-2,5-Pyridinebenzobisoxazole

A mixture of 13.25 g of concentrated orthophosphoric acid (85.9% H₃ PO₄)and 29.75 % of 115% PPA was stirred under reduced pressure at 100° C.for 2.5 hours. The resulting solution was then poured under a stream ofargon at 20° C. into a 100 ml resin kettle containing 10.8621 g(0.050980 mol) of 4,6-diamino-1,3-benzenediol dihydrochloride (1b) thatwas prepared according to the method of Wolfe, et al., Macromolecules,Vol. 14, 909 (1981), recrystallized from aqueous hydrochloric acidcontaining 3 wt % stannous chloride, and dried for 72 hours at 20° C.under reduced pressure immediately before use. The mixture was stirredat 55° C. for 18 hours, at 76° C. for 24 hours under reduced pressure.2,5-pyridinedicarboxylic acid (2i) (8.5720 g, 0.050984 mol) was thenadded under argon flow. Additional P₂ O₅ (31.18 g) was then added. Thesolution was stirred, and heated as follows: 100° C. for 1 hour; 120° C.for 3 hours; 130° C. for 0.5 hours; 140° C. for 0.5 hours; 150° C. for0.5 hours; 185° C. for 48 hours (the dark red solution becamestir-opalescent during the first hour of this last period). Theresulting product was deep red with a metallic luster, exhibitedstir-opalescence, and is further characterized as having a finaleffective P₂ O₅ content of 84% with the --BK--_(n) polymer concentrationbeing 13.4% by weight. The intrinsic viscosity of the polymethyl--BK--_(n) isolated from the reaction product was 4.96 dL/g in MSA at30° C., which corresponds to an average number of recurring units, n, ofapproximately 50.

EXAMPLE 128

The reaction products from Examples 27 and 120 were precipitated inwater and the polymers obtained (polymers --T--_(n) and --V--_(n),respectively) were chopped in a Waring Blender and dried. The reactionproduct from Example 12 was dry-Jet wet spun into fiber (polymer--AI--_(n)) and dried. All of the precipitated polymers and spun fiberof Examples 12, 27, and 120 including as spun fiber (polymer --BI--_(n))produced in Example 117 were tested as follows: the precipitatedpolymers and spun fibers were placed in four of the ten positions in anisothermal aging apparatus developed by SRL Laboratories of Dayton, Ohioand heated at 371° C. in circulating air for 200 hours. The apparatushas ten positions and the weight remaining in each of the positions isrecorded at 20 minute intervals. Each of the polymer samples lostapproximately 14% of their original weight initially indicating thepresence of residual volatile species (e.g., water). The weight lossesdue to isothermal aging of the individual polymers (after the initialweight loss) were as follows:

    ______________________________________                                               Polymer                                                                              Wt % Loss                                                       ______________________________________                                               --[V] .sub.n--                                                                        8.0                                                                   --[BI] .sub.n--                                                                      12.0                                                                   --[T] .sub.n--                                                                       23.0                                                                   --[AI] .sub.n--                                                                      27.0                                                            ______________________________________                                    

The results are shown graphically in FIGS. 1 and 2.

EXAMPLE 129

The samples described in Example 128 were analyzed in a Du Pont 990Thermogravimetric Analyzer at a heating rate of 5° C./min. The weightretention in He and air atmospheres (flow rate=60 ml/min) as a functionof temperature is shown for the four polymers in FIGS. 3, 4 (in He) and5, 6 (in air). The isothermal aging (see FIGS. 1 and 2) of all fourpolymers of Example 128 show a marked improvement especially forpolymers --V--_(n), and --BI--_(n). Polymer --BI--_(n) can be compareddirectly with Wolfe and Loo U.S. Pat. No. 4,225,700. The improvement ispresumed to be caused by the increase in molecular weight and/or themore highly ordered morphology of the resulting polymers/fibers formedfrom compositions of the invention. Thermogravimetric analysis in air(at a heating rate of 10° C./min) was also performed on two blockpolymers of the instant invention; these block polymers were isolatedand dried from the reaction products of Example 73 and 74. The resultsof the TGA are shown in FIG. 2A.

EXAMPLE 130

A mixture of 173.59 g of concentrated orthophosphoric acid (85.5% H₃PO₄) and 414.71 g of 115% PPA was stirred under reduced pressure for 2hours. The resulting solution was then poured at approximately 30° C.under an argon stream into a 2L resin kettle containing 118.70422 g(0.557127 mol) of 4,6-diamino-1,3-benzenediol dihydrochloride (1b) thatwas prepared according to the method of Wolfe and Arnold,Macromolecules, vol. 14, 909 (1981), recrystallized from aqueoushydrochloric acid containing 3 wt % stannous chloride, and dried for 3.5days at 20° C. under reduced pressure immediately before use. Themixture was stirred at 60° C. for 48 hours and 80° C. for 6 hours underreduced pressure. Monomer 2a (92.55800 g, 0.55713 mol) was then addedunder argon flow. Deaerated P₂ O₅ (404.45 g) was added. The mixture wasthen heated at 100° C. for 18 hours, and 185° C. for 29 hours. The darkblue-black solution became stir-opalescent after 1.5 hours at 185° C.The reaction product was deep purple with a golden metallic luster,exhibited stir-opalescence, and was further characterized as having afinal effective P₂ O₅ content of 83.2%, with the --BI--_(n) polymerconcentration being 11.3% by weight. The intrinsic viscosity of thepolymer --BI--_(n) isolated from the reaction product was 20.4 dL/g inMSA at 30° C., which corresponds to an average number of recurringunits, n, of approximately 100.

EXAMPLE 131

The reactor used for the preparation of polymer --AI--_(n) of thisExample was constructed with all wetted parts made of Hastelloy C-276.The working volume was 115L (30 gal). Mixing was provided by fourvertical, stationary baffles attached to the reactor lid and a rotatingassembly with four vertical members. The rotating assembly was driven bya 5 hp-2.5 hp two-speed motor and had a bearing and seal at top andbottom. The reactor was charged with 13.4888 kg (55.0129 mol) of monomer1a and then with 49.1 kg of a PPA prepared from 19.64 kg of 85.8% H₃ PO₄and 29.46 kg of 115% PPA. The reactor was then heated to 60° C. within 1hour and placed under reduced pressure for 20 hours. The P₂ O₅ contentwas then raised to 78.5 % by the addition of 7.751 kg of P₂ O₅ over a2-hour period, which caused the temperature to rise spontaneously to 92°C. After cooling to 68° C., an additional 5.647 kg of P₂ O₅ was added in30 minutes, causing the temperature to rise to 84° C. The mixture wasstirred at 80° C. under reduced pressure for an additional 17 hours, atwhich time all the HCl appeared to have been evolved. Monomer 2a (9.1396kg, 55.015 mol) was then added in four portions. Each portion was addedunder reduced pressure by first adding the monomer to a 12L additionbulb, placing both the reactor and bulb under reduced pressure, and thenopening a ball valve between the two chambers. Additional P₂ O₅ (26.296kg) was then added in two portions according to equation b* to give anintermediate P₂ O₅ content of 86.26% and a final P₂ O₅ content of82.57%. The reaction mixture was then stirred at slow speed overnight at100°-112° C. under an argon atmosphere. Using the faster stirring speed,the mixture was then heated, and samples were removed for intrinsicviscosity determinations according to the following schedule:

    ______________________________________                                        Reaction Time                                                                              Reaction Temperature                                             minutes      °C.     --[AI] --, dL/g                                   ______________________________________                                        0-12         103-112                                                           20          127                                                               27          140                                                               42          159                                                               60          172                                                               73          180                                                               87          183                                                              100          185             7.83                                             120          185            15.33                                             135          187            17.77                                             149          186            20.18                                             165          184            21.80                                             183          179                                                              ______________________________________                                    

The reaction mixture was then cooled to 110° C. over a period of fourhours, at which time the intrinsic viscosity was 24.6 dL/g. The green,opalescent product was then reheated to 130° C. and removed from thereactor for spinning. A sample taken at the end of the removal wasmeasured to have an intrinsic viscosity of 27.26 dL/g. A small samplewas heated at 185° C. for an additional 24 hours, and the intrinsicviscosity rose to 34.11 dL/g.

EXAMPLE 132

A mixture of 34.97 g of PPA (83.8% P₂ O₅) and 15.00 g of H₃ PO₄ wasstirred and heated to 100° C. in a 100-ml 3-necked flask. The flask wasplaced under reduced pressure for 2.0 hours. To a 100-ml resin kettlewas added 21.32 g of 3,4-diaminobenzoic acid.2 HCl. The flask wasdeaerated and flushed with argon. 33.84 g of the above prepared PPAsolvent (having a P₂ O₅ content of 77.32%) was added to the kettle. Thekettle was heated with an oil bath at 50° C. with moderate stirringunder water-aspirator reduced pressure for 1.0 hour. The flask was thenplaced under vacuum-pump reduced pressure for an additional 46.83 hours.The temperature remained at 50° C. for 18.0 hours, at 60° C. for 1.77hours, at 70° C. for 23.81 hours, and at 80° C. for 4.25 hours. At thetime the vacuum was removed, the mixture was riding on the stir blades.Near the end of dehydrochlorination, the mixture was still opaque andthe color was mint green. The P₂ O₅ was added as a powder in twoadditions. The first addition of P₂ O₅ was in the amount of 6.93 g. TheP₂ O₅ was added under argon at 80° C. with stirring. The P₂ O₅ wasincorporated under reduced pressure. Reduced pressure was maintained for18.57 hours. The remaining 14.00 g of P₂ O₅ were added and incorporatedunder reduced pressure with stirring at 80° C. (Total P₂ O₅ =20.93 g.)The amount of P₂ O₅ added was calculated to provide the reaction mixturewith an effective P₂ O₅ content of approximately 85.99% prior to thebeginning of polymerization and an effective P₂ O₅ content ofapproximately 80.94% subsequent to substantially completepolymerization. The mixture was heated to a final temperature of 200° C.following the heating schedule outlined below.

    ______________________________________                                        Temperature                                                                              Time                                                               (°C.)                                                                             (Hours)     Observations                                           ______________________________________                                         90        0.73                                                               110        0.63        Foamy; darker green;                                                          vacuum removed.                                        120        0.72        Pea-soup green;                                                               more fluid; clearing.                                  130        0.88                                                               142        0.50                                                               152        0.17        Mixture clearer with                                                          small particles                                                               present.                                               161        0.27        Mixture full of bubbles.                               169        0.45                                                               182        0.83                                                               200        20.79                                                              ______________________________________                                    

A sample of the reaction product was stretchable, fibrous, and turnedwhite as it was drawn. The fiber was precipitated in water. The fiberand a nonprecipitated sample were birefringent at rest at roomtemperature under crossed polars. The clear green dope appeared hazy asit was cooled. The intrinsic viscosity of the reaction product was 6.58dL/g in MSA at 30° C. and the polymer concentration was 15.90%. Thepolymer obtained is of the following structure: ##STR783##

EXAMPLE 133

A mixture of 14.71 g of concentrated orthophosphoric acid (85.9% H₃ PO₄)and 22.64 g of 115% PPA was stirred under reduced pressure at 100° C.for 2.5 hours. The resulting solution was then poured at approximately25° C. under a stream of argon into a 100 ml resin kettle containing11.04664 g (0.045053 mol) of 2,5-diamine-1,4-benzenedithioldihydrochloride (1a). The mixture was stirred under reduced pressure at50° C. for 2 hours; 60° C. for 16 hours, and 80° C. for 12.5 hours tocomplete the dehydrochlorination. Monomer 2a (7.4863 g, 0.045001 mol)was then added under an argon flow. P₂ O₅ (48.29 g) was then added. Themixture was heated at 100° C. for 3 hours and at 185° C. for 33 hours.The resulting reaction product was light green with an iridescentluster, exhibited stir-opalescence, and was further characterized ashaving a final effective P₂ O₅ content of 83.6% with the --AI--_(n)polymer concentration being 11.6 wt %. The intrinsic viscosity of thepolymer --AI--_(n) isolated from the reaction product was 47.8 dL/g inMSA at 30° C., which corresponds to an average number of recurringunits, n, of approximately 140.

The physical properties of as spun and heat treated fibers formed fromcompositions of Examples 117, 119, 121, 123, 124, 125, and 126 above areshown in Tables 29 and 30 below.

                  TABLE 29                                                        ______________________________________                                               EXAMPLES                                                                        Example  --[BI] .sub.n--                                                                        --[BI] .sub.n--                                                                      --[V] .sub.n--                                                                       --[V] .sub.n--                       CONDITION                                                                              No.:     117      119    121    123                                  ______________________________________                                        Polymer dope                                                                   1. Intrinsic 23.9     24.4     13.8   12.0                                   Viscosity                                                                     (dL/g)                                                                         2. P.sub.2 O.sub.5                                                                         82.3     83.2     82.2   83.8                                   Content (%)                                                                    3. Polymer   13.3     13.8     16.7   16.9                                   Concentration (%)                                                             Spinning Conditions                                                            4. Spin      6.1:1    53:1     6.6:1  145:1                                  Draw Ratio                                                                     5. Spin Tem- 63       70       65     90                                     perature (°C.)                                                          6. Air Gap   21       20.3     31.7   20.3                                   Distance (cm)                                                                  7. Jet Di-     0.381   0.25      0.381                                                                               0.25                                  ameter (mm)                                                                    8. Dope      *2        1.17    *3.4   *3.4                                   pressure                                                                      (MPa)                                                                         As Spun Fiber Properties                                                       9. Tensile    2.96      3.12    2.34   3.57                                  psi Strength                                                                  (GPa)                                                                         10. Single    --       --       --      5.01                                  break Tensile                                                                 Strength                                                                      (GPa)                                                                         highest value                                                                 11. Modulus   89.6     303      41-96  133                                    psi (GPa)                                                                     12. Elonga-   4.2-6    --       --      3.3                                   tion %                                                                        13. Fiber     33       --       37-76  16                                     diameter                                                                      (Micrometers)                                                                 Heat Treatment Conditions                                                     14. Tempera-  500      450      500    --                                     ture (°C.)                                                             15. Time      60       30       60     --                                     (seconds)                                                                     16. Stretch   --       2         7.5   --                                     factor (%)                                                                    17. Atmos-    Nitrogen Air      Nitrogen                                                                             --                                     phere                                                                         condition                                                                     Post Heat Treatment Fiber Properties                                          18. Tensile   3.45     3.07     2.34   --                                     Strength                                                                      (GPa)                                                                         19. Modulus   317      410      136    --                                     (GPa)                                                                         20. Elonga-   1.8-2.4  --       --     --                                     tion (%)                                                                      21. Fiber     31.4     --       --     --                                     Diameter                                                                      (Micrometers)                                                                 22. Visual    uniform  non-     --     --                                                            uniform                                                ______________________________________                                         *denotes approximate values                                              

                  TABLE 30                                                        ______________________________________                                                   EXAMPLES                                                                        Example  --[V] .sub.n--                                                                         --[V] .sub.n--                                                                       --[V] .sub.n--                          CONDITIONS   No.:     124      125    126                                     ______________________________________                                        Polymer dope                                                                   1. Intrinsic Viscosity                                                                         12.0     12.0     12.0                                      (dL/g)                                                                         2. P.sub.2 O.sub.5 Content (%)                                                                 83.8     83.8     83.8                                       3. Polymer Con-  16.9     16.9     16.9                                      centration (%)                                                                Spinning Conditions                                                            4. Spin Draw Ratio                                                                             125:1    100:1    17.2:1                                     5. Spin Temperature                                                                            90       90       80                                        (°C.)                                                                   6. Air Gap Distance                                                                            20.3     20.3     31.7                                      (cm)                                                                           7. Jet Diameter (mm)                                                                            0.25     0.25     0.25                                      8. Dope pressure *3.4     *3.4     *3.4                                      (MPa)                                                                         As Spun Fiber Properties                                                       9. Tensile Strength (GPa)                                                                       2.57     2.83     2.76                                     10. Single break Ten-                                                                            3.38     3.29    --                                        sile Strength (GPa)                                                           highest value                                                                 11. Modulus (GPa) 79       61       41                                        12. Elongation (%)                                                                               4.6      4.8     --                                        13. Fiber diameter                                                                              19       21       45                                        (micrometers)                                                                 Heat Treatment Conditions                                                     14. Temperature (°C.)                                                                    450      400      500                                       15. Time (seconds)                                                                              30       30       30                                        16. Stretch factor (%)                                                                           4.37     4.37     1.28                                     17. Atmosphere    Nitrogen Nitrogen Nitrogen                                  condition                                                                     Post Heat Treatment Fiber Properties                                          18. Tensile Strength                                                                             2.85     3.34     2.62                                     (GPa)                                                                         19. Single break ten-                                                                            4.94     3.76     3.00                                     sile Strength (GPa)                                                           highest value                                                                 20. Modulus (GPa) 119      115      144                                       21. Elongation (%)                                                                               2.5      3.6      2.2                                      22. Fiber Diameter                                                                               19.15   --       42.7                                      (Micrometers)                                                                 ______________________________________                                         *denotes approximate values                                              

As exemplified in the examples above, the compositions of the inventionare prepared in batch fashion but continuous procedures may be employed.

Some process and product benefits as a result of better control ofcertain process parameters such as shear and temperature in a continuousprocess are: (1) a more homogeneous products of reaction as a result ofa much higher order of magnitude of mixing; (2) higher throughputs; (3)and improved economics.

Another advantage of continuous processing is that the resultingreaction products can be blended in essentially all portions with ocherreaction products of different polymer type and/or reaction products atdifferent stages of reaction.

In a continuous process, the aforementioned dehydrochlorination step of"Stage One" and monomer-P₂ O₅ addition of "Stage Two" are conducted at atemperature not to exceed about 100° C. in a batch reactor preferably ofthe type described in Example 116. "Stage Three" of the invention can beconducted in a motionless (static) mixer. Such mixers for paste and veryviscous materials are described in "Chemical Engineers' Handbook", R. H.Perry et al., McGraw-Hill Kogakusha, LTD., International StudentEdition, pp. 19-24, (1973); "Fluid Mixing Technology", by James Y.Oldshue, McGraw-Hill Publishing Company, pp. 431-438, (1983); and Groutet al., U.S. Pat. No.: 3,800,985. These publications and patent areincorporated herein by reference. The reaction mixture of "Stage Two" isfed from an outlet of the batch reactor through a constant displacementpump to a static mixer (tubular reactor) preferably of the typedescribed in U.S. Pat. No. 3,800,985 where the first mixing element isheated at a temperature between about 140° C. to about 185° C. Thesecond and subsequent intermediate mixing elements are heated attemperatures between about 165° C. and about 200° C. The last mixingelements are heated at temperatures between about 80° C., and about 200°C. depending on the desired temperature selected for spinning theparticular extended chain polymer employed.

In order to avoid interruptions in the continuous process, two or morebatch reactors (for conducting "Stage One" and "Stage Two") areconnected to the static mixer (tubular reactor) in parallel arrayfashion so as to lead said tubular reactor in time-wise sequence.Preferably, "Stages One and "Stage Two" can be conducted in an emptiedbatch reactor without the need for clean-up. The volume requirement ofthe tubular reactor is a function of the size and number of the batchreactor array, the desired (mixing elements) residence time, and thedesired flow rate.

Such a continuous process is especially suitable for the preparation ofblock copolymers of the present invention. Block copolymers can be madeby admixing a second reaction mixture after the first reaction mixturehas passed through an intermediate number of mixing elements.

A very important aspect of the continuous process as well as for thebatch process which must be emphasized is that "Stage One", "Stage Two",and "Stage Three" of the invention must be conducted within the shadedphosphorus pentoxide content profile area bounded by ABCDEFGHI of FIG.14. This is unrealized by the art.

                  APPENDIX                                                        ______________________________________                                        General Structure Reference                                                   ______________________________________                                        [A]                                                                                 ##STR784##                                                              [B]                                                                                 ##STR785##                                                              [C]                                                                                 ##STR786##                                                              [D]                                                                                 ##STR787##                                                              [E]                                                                                 ##STR788##                                                              [F]                                                                                 ##STR789##                                                              [G]                                                                                 ##STR790##                                                              [H]                                                                                 ##STR791##                                                              [I]                                                                                 ##STR792##                                                              [J]                                                                                 ##STR793##                                                              [K]                                                                                 ##STR794##                                                              [L]                                                                                 ##STR795##                                                              [M]                                                                                 ##STR796##                                                              [N]                                                                                 ##STR797##                                                              [O]                                                                                 ##STR798##                                                              [P]                                                                                 ##STR799##                                                              [Q]                                                                                 ##STR800##                                                              [R]                                                                                 ##STR801##                                                              [S]                                                                                 ##STR802##                                                              [T]                                                                                 ##STR803##                                                              [U]                                                                                 ##STR804##                                                              [V]                                                                                 ##STR805##                                                              [W]                                                                                 ##STR806##                                                              [X]                                                                                 ##STR807##                                                              [Y]                                                                                 ##STR808##                                                              [Z]                                                                                 ##STR809##                                                              [A']                                                                                ##STR810##                                                              [B']                                                                                ##STR811##                                                              [C']                                                                                ##STR812##                                                              [D']                                                                                ##STR813##                                                              [E']                                                                                ##STR814##                                                              [F']                                                                                ##STR815##                                                               [G']                                                                               ##STR816##                                                               [H' ]                                                                              ##STR817##                                                              [I']                                                                                ##STR818##                                                                    ##STR819##                                                               [J']                                                                               ##STR820##                                                                    ##STR821##                                                                    ##STR822##                                                               [K']                                                                               ##STR823##                                                                    ##STR824##                                                              [L']                                                                                ##STR825##                                                              [M']                                                                                ##STR826##                                                                    ##STR827##                                                               [N']                                                                               ##STR828##                                                                    ##STR829##                                                              [O']                                                                                ##STR830##                                                              [P']                                                                                ##STR831##                                                              [Q']                                                                                ##STR832##                                                              [R']                                                                                ##STR833##                                                              [S']                                                                                ##STR834##                                                              [T']                                                                                ##STR835##                                                              [U']                                                                                ##STR836##                                                              [V']                                                                                ##STR837##                                                              [W']                                                                                ##STR838##                                                              [X']                                                                                ##STR839##                                                              [Y']                                                                                ##STR840##                                                              [Z']                                                                                ##STR841##                                                              [A"]                                                                                ##STR842##                                                              [B"]                                                                                ##STR843##                                                              [C"]                                                                                ##STR844##                                                              [D"]                                                                                ##STR845##                                                              [E"]                                                                                ##STR846##                                                              [F"]                                                                                ##STR847##                                                              [G"]                                                                                ##STR848##                                                              [H"]                                                                                ##STR849##                                                              [I"]                                                                                ##STR850##                                                              [J"]                                                                                ##STR851##                                                              [K"]                                                                                ##STR852##                                                              [L"]                                                                                ##STR853##                                                              [M"]                                                                                ##STR854##                                                              [N"]                                                                                ##STR855##                                                              [O"]                                                                                ##STR856##                                                              [P"]                                                                                ##STR857##                                                              [Q"]                                                                                ##STR858##                                                              [R"]                                                                                ##STR859##                                                              [S"]                                                                                ##STR860##                                                              [T"]                                                                                ##STR861##                                                              [U"]                                                                                ##STR862##                                                              [V"]                                                                                ##STR863##                                                              [W"]                                                                                ##STR864##                                                              [X"]                                                                                ##STR865##                                                              [Y"]                                                                                ##STR866##                                                              [Z"]                                                                                ##STR867##                                                              ______________________________________                                    

While certain features of this invention have been described in detailwith respect to various embodiments thereof, it will, of course, beapparent that other modifications can be made within the spirit andscope of this invention, and it is not intended to limit the inventionto the exact details shown above except insofar as they are defined inthe following claims.

What we claim is:
 1. A fiber containing a polybenzoxazole polymer orcopolymer and having an average tensile strength of at least 2.96 GPa.2. A fiber of claim 1 wherein the polymer or copolymer comprisespredominantly repeating units represented by the Formula: ##STR868##wherein: each Ar³ is independently an aromatic moiety; andeach X₃ is anoxygen atom.
 3. The fiber of claim 2 wherein Ar³ is a trivalent benzenemoiety.
 4. The fiber of claim 3 wherein the fiber has an average tensilestrength of at least about 3.57 GPa.
 5. The fiber of claim 1 wherein thefiber comprises predominantly repeating units represented by theFormula: ##STR869## wherein: X₁ and X₂ are each an oxygen atom;Ar¹ is anaromatic moiety; and Y² is a bivalent organic moiety.
 6. The fiber ofclaim 5 wherein the fiber has an average tensile strength of at leastabout 3.12 GPa.
 7. The fiber of claim 5 wherein each Ar¹ contains atetravalent benzene moiety and each Y² contains a divalent benzenemoiety.
 8. The fiber of claim 5 wherein the polymer or copolymerconsists essentially of repeating units independently represented by theone of the Formulae: ##STR870##
 9. A fiber having an average tensilemodulus of at least 133 GPa and containing a polybenzoxazole polymer orcopolymer that comprises predominantly repeating units represented bythe Formula: ##STR871## wherein: each Ar³ is independently an aromaticmoiety; andeach X₃ is an oxygen atom.
 10. A fiber of claim 9 whereineach Ar³ is an trivalent benzene moiety.
 11. A fiber having a tensilemodulus of at least 317 GPa and containing a polymer or copolymer thatpredominantly comprises repeating units represented by the Formula:##STR872## ##STR873## wherein: X₁ and X₂ are each an oxygen atom;Ar¹ isan aromatic moiety; and Y² is a bivalent organic moiety.
 12. The fiberof claim 11 wherein each Ar¹ is a tetravalent benzene moiety and each Y²contains a divalent benzene moiety.
 13. The fiber of claim 11 whereinthe fiber has an average tensile modulus of at least about 410 GPa. 14.The fiber of claim 11 wherein the polymer or copolymer consistsessentially of repeating units represented by the Formula: ##STR874##